U.S. patent application number 14/680364 was filed with the patent office on 2016-01-07 for compositions and polymer composites prepared from the same.
The applicant listed for this patent is SAMSUNG ELECTRONICS CO., LTD.. Invention is credited to Eun Joo JANG, Hyun A. KANG, Jeong Hee LEE, Na Youn WON.
Application Number | 20160005932 14/680364 |
Document ID | / |
Family ID | 55017620 |
Filed Date | 2016-01-07 |
United States Patent
Application |
20160005932 |
Kind Code |
A1 |
LEE; Jeong Hee ; et
al. |
January 7, 2016 |
COMPOSITIONS AND POLYMER COMPOSITES PREPARED FROM THE SAME
Abstract
A composition including: a monomer mixture including a first
monomer having at least two thiol groups at its terminal end and a
second monomer having at least two carbon-carbon unsaturated
bond-containing groups at its terminal end; and at least one
additive selected from a zinc compound, an indium compound,
ascorbic acid or a salt thereof, citric acid or a salt thereof, a
tocopherol, and a tocotrienol.
Inventors: |
LEE; Jeong Hee;
(Seongnam-si, KR) ; KANG; Hyun A.; (Suwon-si,
KR) ; JANG; Eun Joo; (Suwon-si, KR) ; WON; Na
Youn; (Suwon-si, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG ELECTRONICS CO., LTD. |
Suwon-si |
|
KR |
|
|
Family ID: |
55017620 |
Appl. No.: |
14/680364 |
Filed: |
April 7, 2015 |
Current U.S.
Class: |
257/98 ;
252/182.17; 252/301.36; 524/111; 524/320; 524/399; 524/432;
524/439; 524/81 |
Current CPC
Class: |
C09K 11/70 20130101;
C08K 3/22 20130101; C09K 11/703 20130101; C08K 2003/2296 20130101;
C08K 5/1535 20130101; C08K 2003/0893 20130101; C09K 11/565
20130101; C08K 3/08 20130101; C09K 11/02 20130101; C08K 5/56
20130101; H01L 51/502 20130101; C08K 5/098 20130101; C09K 11/025
20130101; C08K 5/092 20130101 |
International
Class: |
H01L 33/50 20060101
H01L033/50; C09K 11/70 20060101 C09K011/70; C08K 3/22 20060101
C08K003/22; C08K 5/56 20060101 C08K005/56; C08K 5/1535 20060101
C08K005/1535; C08K 5/092 20060101 C08K005/092; C08K 5/098 20060101
C08K005/098; C09K 11/02 20060101 C09K011/02; C08K 3/08 20060101
C08K003/08 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 1, 2014 |
KR |
10-2014-0082045 |
Claims
1. A composition comprising: a monomer mixture comprising a first
monomer comprising at least two thiol groups at its terminal end
and a second monomer comprising at least two carbon-carbon
unsaturated bond-containing groups at its terminal end; and at
least one additive selected from a zinc compound, an indium
compound, ascorbic acid or a salt thereof, citric acid or a salt
thereof, a tocopherol, and a tocotrienol.
2. The composition of claim 1, further comprising a light emitting
particle selected from a Group II-VI compound semiconductor
nanocrystal, a Group III-V compound semiconductor nanocrystal, a
Group IV-VI compound semiconductor nanocrystal, and a Group IV
compound semiconductor nanocrystal.
3. The composition of claim 2, further comprising at least one
light emitting particle selected from a metal nanocrystal, a metal
oxide nanocrystal, a phosphor, and a pigment.
4. The composition of claim 1, wherein the first monomer is
represented by Chemical Formula 1: [R.sup.1 .sub.k1L.sub.1
Y.sub.1--(SH).sub.m].sub.k2 Chemical Formula 1 wherein, in Chemical
Formula 1, R.sup.1 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; --NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group, L.sub.1 is selected from
a carbon atom, a substituted or unsubstituted C1 to C30 alkylene
group, a substituted or unsubstituted C6 to C30 cycloalkylene
group, a substituted or unsubstituted C6 to C30 arylene group, or a
substituted or unsubstituted C6 to C30 heteroarylene group, and a
C1 to C30 alkylene group, wherein at least one non-adjacent
--CH.sub.2-- group is replaced by --SO.sub.2--, --C(.dbd.O)--,
--O--, --S--, --SO--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 alkyl group, or a combination thereof,
Y.sub.1 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof, m is an
integer of 1 or more, k1 is 0 or an integer of 1 or more, k2 is an
integer of 1 or more, wherein the sum of m and k2 is an integer of
3 or more, provided that m does not exceed the valence of Y.sub.1,
and provided that the sum of k1 and k2 does not exceed the valence
of L.sub.1.
5. The composition of claim 1, wherein the second monomer is
represented by Chemical Formula 2: [R.sup.2 .sub.k3L.sub.2
Y.sub.2--(X).sub.n].sub.k4 Chemical Formula 2 wherein, in Chemical
Formula 2, X is selected from an aliphatic organic group comprising
a carbon-carbon double bond or a carbon-carbon triple bond, an
aromatic organic group comprising a carbon-carbon double bond or a
carbon-carbon triple bond, and an alicyclic organic group
comprising a carbon-carbon double bond or a carbon-carbon triple
bond, R.sup.2 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C3 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group, L.sub.2 is selected from
a carbon atom, a substituted or unsubstituted C1 to C30 alkylene
group, a substituted or unsubstituted C6 to C30 cycloalkylene
group, a substituted or unsubstituted C6 to C30 arylene group, and
a substituted or unsubstituted C3 to C30 heteroarylene group,
Y.sub.2 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, and --NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, or a combination thereof, n is
an integer of 1 or more, k3 is an integer of 0 or more, k4 is an
integer of 1 or more, wherein the sum of n and k4 is an integer of
3 or more, provided that n does not exceed the valence of Y.sub.2,
and provided that the sum of k3 and k4 does not exceed the valence
of L.sub.2.
6. The composition of claim 4, wherein the first monomer of
Chemical Formula 1 comprises a monomer of Chemical Formula 1-1:
##STR00029## wherein, in Chemical Formula 1-1, L1' is selected from
carbon; a substituted or unsubstituted C6 to C30 tetravalent
arene-derived group; a substituted or unsubstituted C3 to C30
tetravalent heteroarene-derived group; a substituted or
unsubstituted C3 to C30 tetravalent cycloalkane-derived group; and
a substituted or unsubstituted C3 to C30 heterocycloalkane-derived
group, each of Y.sub.a to Y.sub.d is independently selected from a
single bond; a substituted or unsubstituted C1 to C30 alkylene
group; a substituted or unsubstituted C2 to C30 alkenylene group;
and a C1 to C30 alkylene group or a C2 to C30 alkenylene group,
wherein at least one --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, --NR--, wherein R is hydrogen
or a C1 to C10 linear or branched alkyl group, or a combination
thereof, and R.sub.a to R.sub.d are each independently selected
from R.sup.1 of Chemical Formula 1 or SH, provided that at least
two groups selected from R.sub.a to R.sub.d are SH.
7. The composition of claim 6, wherein the first monomer of
Chemical Formula 1 is at least one selected from trimethylolpropane
tris(3-mercaptopropionate) of Chemical Formula 1-2, pentaerythritol
tetrakis(3-mercaptopropionate) of Chemical Formula 1-3,
pentaerythritol tetrakis(2-mercaptoacetate) of Chemical Formula
1-4, tris[2-(3-mercaptopropinonyloxy)alkyl]isocyanurate of Chemical
Formula 1-5, a compound of Chemical Formula 1-6, a compound of
Chemical Formula 1-7, and a compound of Chemical Formula 1-8:
##STR00030## wherein, in Chemical Formula 1-5, R is a substituted
or unsubstituted C1 to C10 alkylene; ##STR00031## wherein n is an
integer of 1 to 20; ##STR00032## wherein n is an integer of 1 to
20; and ##STR00033## wherein n is an integer of 1 to 20.
8. The composition of claim 5, wherein, in Chemical Formula 2, X is
selected from an acrylate group; a methacrylate group; a C2 to C30
alkenyl group; a C2 to C30 alkynyl group; a substituted or
unsubstituted C3 to C30 alicyclic organic group having a
carbon-carbon double bond or a carbon-carbon triple bond in the
ring; a substituted or unsubstituted C3 to C30 heterocycloalkyl
group having a carbon-carbon double bond or a carbon-carbon triple
bond in the ring; a C3 to C30 alicyclic organic group substituted
with a C2 to C30 alkenyl group or a C2 to C30 alkynyl group; and a
C3 to C30 heterocycloalkyl group substituted with a C2 to C30
alkenyl group or a C2 to C30 alkynyl group.
9. The composition of claim 5, wherein the substituted or
unsubstituted C3 to C30 alicyclic organic group comprising a
carbon-carbon double bond or a carbon-carbon triple bond in the
ring is selected from a norbornene group, a maleimide group, a
nadimide group, and a tetrahydrophthalimide group.
10. The composition of claim 5, wherein the second monomer is at
least one selected from a C4 to C100 diallyl compound, a C4 to C100
triallyl compound, a C4 to C100 diallyl ether compound, a C4 to
C100 triallyl ether compound, a C4 to C100 di(meth)acrylate
compound, a C4 to C100 tri(meth)acrylate compound, and a C4 to C100
divinyl ether compound.
11. The composition of claim 5, wherein in Chemical Formula 2,
L.sup.2 is selected from a group comprising a pyrrolidine moiety, a
tetrahydrofuran moiety, a pyridine moiety, a pyrimidine moiety, a
piperidine moiety, a triazine moiety, and an isocyanurate
moiety.
12. The composition of claim 5, wherein the second monomer of
Chemical Formula 2 is selected from a compound represented by
Chemical Formula 2-1, Chemical Formula 2-2, and Chemical Formula
2-3: ##STR00034## wherein, in Chemical Formulae 2-1 and 2-2, each
of Z.sub.1 to Z.sub.3 are independently *--Y.sub.2--X, as defined
in Chemical Formula 2; ##STR00035## wherein, in Chemical Formula
2-3, L.sub.2' is selected from carbon; a substituted or
unsubstituted C1 to C30 tetravalent alkane-derived group; a
substituted or unsubstituted C2 to C30 tetravalent alkene-derived
group; a C1 to C30 tetravalent alkyne-derived group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, a C6 to C10 cycloalkylene group, or
a combination thereof; a C2 to C30 tetravalent alkene-derived
group, wherein at least one --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, --NR--, wherein R is hydrogen
or a C1 to C10 linear or branched alkyl group, a C6 to C10
cycloalkylene group, or a combination thereof; a substituted or
unsubstituted C6 to C30 tetravalent arene-derived group; a
substituted or unsubstituted C3 to C30 tetravalent
heteroarene-derived group; a substituted or unsubstituted C3 to C30
tetravalent cycloalkane-derived group; and a substituted or
unsubstituted C3 to C30 derived heterocycloalkane-derived group,
each of Y.sub.a to Y.sub.d is independently selected from a single
bond; a substituted or unsubstituted C1 to C30 alkylene group; a
substituted or unsubstituted C2 to C30 alkenylene group; and a C1
to C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof, and
R'.sub.a to R'.sub.d are R.sup.2 of Chemical Formula 2 or X of
Chemical Formula 2, provided that at least two groups selected from
R'.sub.a to R'.sub.d are X of Chemical Formula 2.
13. The composition of claim 5, wherein the second monomer
comprises at least one selected from a compound of Chemical Formula
2-4, a compound of Chemical Formula 2-5, a compound of Chemical
Formula 2-6, a compound of Chemical Formula 2-7, a compound of
Chemical Formula 2-8, a compound of Chemical Formula 2-9, a
compound of Chemical Formula 2-10, a compound of Chemical Formula
2-11, a compound of Chemical Formula 2-12, a compound of Chemical
Formula 2-13, a compound of Chemical Formula 2-14, and a compound
of Chemical Formula 2-15: ##STR00036## wherein, in Chemical Formula
2-7, R.sub.1 is selected from a C1 to C20 alkylene group and a C1
to C20 alkylene group, wherein at least one --CH.sub.2-- group is
replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--,
--S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof, and R.sub.2 is selected from
hydrogen and a methyl group; ##STR00037## wherein, in Chemical
Formula 2-8, R is a C1 to C10 alkyl group; ##STR00038## wherein, in
Chemical Formula 2-9, A is a C1 to C10 alkyl group or a hydroxy
group, R.sub.1 is selected from a single bond, a C1 to C20 alkylene
group, and a C1 to C20 alkylene, wherein at least one --CH.sub.2--
group is replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--,
--S--, --S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof, and R.sub.2 is selected from
hydrogen and a methyl group; ##STR00039## wherein, in Chemical
Formula 2-10, R.sub.1 is selected from a single bond, a C1 to C20
alkylene, and a C1 to C20 alkylene, wherein at least one
--CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof, and
R.sub.2 is selected from hydrogen and a methyl group; ##STR00040##
wherein, in Chemical Formula 2-11, R is selected from a single bond
and a C1 to C20 alkylene or a C1 to C20 alkylene, wherein at least
one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O), --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof,
##STR00041## wherein, in Chemical Formula 2-12, R is a C1 to C20
alkylene or a C1 to C20 alkylene, wherein at least one --CH.sub.2--
group is replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--,
--S--, --S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof, ##STR00042##
14. The composition of claim 1, wherein the monomer mixture further
comprises at least one of a third monomer having one thiol group at
its terminal end and a fourth monomer having one carbon-carbon
unsaturated bond-containing group at its terminal end.
15. The composition of claim 1, wherein the zinc compound comprises
at least one selected from a zinc inorganic acid salt comprising a
counter ion with a pKa of at least 3, a zinc halide, a zinc oxide,
a zinc organic acid salt, a zinc metal, and a dialkyl zinc, and the
indium compound comprises at least one selected from an indium
inorganic salt comprising a counter ion with a pKa of at least 3,
an indium halide, an indium oxide, an indium organic acid salt, an
indium metal, and a dialkyl indium.
16. The composition of claim 1, wherein the composition comprises
the additive in an amount of about 10.sup.-6 parts by weight to
about 10 parts by weight based on 100 parts by weight of the
monomer mixture.
17. The composition of claim 2, wherein the composition comprises
the light emitting particle in an amount of about 0.1 to about 20
parts by weight based on 100 parts by weight of the monomer
mixture.
18. The composition of claim 1, wherein in the monomer mixture, the
first monomer and the second monomer are present in such amounts
that a mole ratio of the thiol group of the first monomer and the
carbon-carbon unsaturated bond of the second monomer is about
1:about 0.75 to about 3.
19. A polymer composite comprising: a thiol-ene cross-linking
polymerization product of a first monomer comprising at least two
thiol groups at its terminal end and a second monomer comprising at
least two carbon-carbon unsaturated bond-containing groups at its
terminal end; and at least one additive selected from a zinc
compound, an indium compound, ascorbic acid or a salt thereof,
citric acid or a salt thereof, a tocopherol, and a tocotrienol.
20. The polymer composite of claim 19, further comprising a light
emitting particle selected from a Group II-VI compound
semiconductor nanocrystal, a Group III-V compound semiconductor
nanocrystal, a Group IV-VI compound semiconductor nanocrystal, and
a Group IV compound semiconductor nanocrystal.
21. The polymer composite of claim 19, further comprising at least
one light emitting particle selected from a metal nanocrystal, a
metal oxide nanocrystal, a phosphor, and a pigment.
22. The polymer composite of claim 19, wherein the first monomer is
represented by Chemical Formula 1: [R.sup.1 .sub.k1L.sub.1
Y.sub.1--(SH).sub.m].sub.k2 Chemical Formula 1 wherein, in Chemical
Formula 1, R.sup.1 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; --NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group, L.sub.1 is selected from
a carbon atom, a substituted or unsubstituted C1 to C30 alkylene
group, a substituted or unsubstituted C6 to C30 cycloalkylene
group, a substituted or unsubstituted C6 to C30 arylene group, or a
substituted or unsubstituted C6 to C30 heteroarylene group, and a
C1 to C30 alkylene group, wherein at least one non-adjacent
--CH.sub.2-- group is replaced by --SO.sub.2--, --C(.dbd.O)--,
--O--, --S--, --SO--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 alkyl group, or a combination thereof,
Y.sub.1 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof, m is an
integer of 1 or more, k1 is 0 or an integer of 1 or more, k2 is an
integer of 1 or more, wherein the sum of m and k2 is an integer of
3 or more, provided that m does not exceed the valence of Y.sub.1,
and provided that the sum of k1 and k2 does not exceed the valence
of L.sub.1; and the second monomer is represented by Chemical
Formula 2: [R.sup.2 .sub.k3L.sub.2 Y.sub.2--(X).sub.n].sub.k4
Chemical Formula 2 wherein, in Chemical Formula 2, X is selected
from an aliphatic organic group comprising a carbon-carbon double
bond or a carbon-carbon triple bond, an aromatic organic group
comprising a carbon-carbon double bond or a carbon-carbon triple
bond, and an alicyclic organic group comprising a carbon-carbon
double bond or a carbon-carbon triple bond, R.sup.2 is selected
from hydrogen; a substituted or unsubstituted C1 to C30 linear or
branched alkyl group; a substituted or unsubstituted C6 to C30 aryl
group; a substituted or unsubstituted C7 to C30 arylalkyl group; a
substituted or unsubstituted C3 to C30 heteroaryl group; a
substituted or unsubstituted C4 to C30 heteroarylalkyl group; a
substituted or unsubstituted C3 to C30 cycloalkyl group; a
substituted or unsubstituted C3 to C30 heterocycloalkyl group; a C1
to C10 alkoxy group; a hydroxy group; NH.sub.2; --NRR', wherein R
and R' are independently hydrogen or a C1 to C30 linear or branched
alkyl group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group), L.sub.2 is selected from
a carbon atom, a substituted or unsubstituted C1 to C30 alkylene
group, a substituted or unsubstituted C6 to C30 cycloalkylene
group, a substituted or unsubstituted C6 to C30 arylene group, and
a substituted or unsubstituted C3 to C30 heteroarylene group,
Y.sub.2 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, (wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group), --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof, n is an
integer of 1 or more, k3 is an integer of 0 or more, k4 is an
integer of 1 or more, wherein the sum of n and k4 is an integer of
3 or more, provided that n does not exceed the valence of Y.sub.2,
and provided that the sum of k3 and k4 does not exceed the valence
of L.sub.2.
23. The polymer composite of claim 19, wherein the zinc compound
comprises at least one selected from a zinc inorganic acid salt
comprising a counter ion having pKa of 3 or more, a zinc organic
acid salt, a zinc halide, a zinc oxide, a zinc metal, and a dialkyl
zinc, and the indium compound comprises at least one selected from
an indium inorganic acid salt comprising a counter ion having pKa
of 3 or more, an indium organic acid salt, an indium halide, an
indium oxide, an indium metal, and a dialkyl indium.
24. A film comprising the polymer composite of claim 19.
25. The film of claim 24, further comprising a barrier film
contacting a surface of the composite.
26. An electronic device comprising the film of claim 24.
27. The electronic device of claim 26, wherein the electronic
device is at least one selected from a display, a light emitting
device, a memory device, a laser device, and a solar cell.
28. The electronic device of claim 26, wherein the light emitting
device comprises a light source, and wherein the film is positioned
on the light source.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to Korean Patent
Application No. 10-2014-0082045 filed in the Korean Intellectual
Property Office on Jul. 1, 2014, and all the benefits accruing
therefrom under 35 U.S.C. .sctn.119, the content of which is
incorporated herein in its entirety by reference.
BACKGROUND
[0002] 1. Field
[0003] A composition and a polymer composite prepared from the same
are disclosed.
[0004] 2. Description of the Related Art
[0005] Light emitting particles may be dispersed in an organic or
inorganic host matrix, and the resulting composite may be applied
to various display devices. For example, semiconductor
nanocrystals, also known as quantum dots, may be dispersed in a
host matrix of a polymer or an inorganic material, and the
resulting entity may be used as a photoconversion layer in a light
emitting diode (LED). Recently, a quantum dot enhancement film
(QDEF) obtained by dispersing the quantum dots in a polymer film
has drawn attention as a tool capable of improving image quality of
a liquid crystal display.
[0006] On the other hand, the semiconductor nanocrystals have low
luminous efficiency and brightness due to oxidation. However, when
a polymer obtained from a mixture of a thiol monomer and a monomer
having a carbon-carbon unsaturated bond (hereinafter referred to as
a thiol-ene system) is used as a host matrix for the semiconductor
nanocrystals, degradation of the luminous efficiency and luminance
may be decreased. However, the thiol-ene system generally has poor
storage stability.
[0007] Therefore, there remains a need in a thiol-ene a thiol-ene
system having improved storage stability
SUMMARY
[0008] An embodiment provides a thiol-ene system having improved
storage stability.
[0009] Another embodiment provides a polymer composite prepared
from the thiol-ene system.
[0010] Yet another embodiment provides a film including the polymer
composite prepared from the thiol-ene system and an electronic
device including the same.
[0011] In an embodiment, a composition includes: a monomer mixture
including a first monomer having at least two thiol groups at its
terminal end and a second monomer having at least two carbon-carbon
unsaturated bond-containing groups at its end; and
[0012] at least one additive selected from a zinc compound, an
indium compound, ascorbic acid or a salt thereof, citric acid or a
salt thereof, a tocopherol, and a tocotrienol.
[0013] The composition may further include a light emitting
particle selected from a Group II-VI compound semiconductor
nanocrystal, a Group III-V compound semiconductor nanocrystal, a
Group IV-VI compound semiconductor nanocrystal, and a Group IV
compound semiconductor nanocrystal.
[0014] The composition may further include a light emitting
particle selected from at least one of a metal nanocrystal, a metal
oxide nanocrystal, a phosphor, and a pigment.
[0015] The first monomer may be represented by Chemical Formula
1.
[R.sup.1 .sub.k1L.sub.1 Y.sub.1--(SH).sub.m].sub.k2 Chemical
Formula 1
[0016] In Chemical Formula 1,
[0017] R.sup.1 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; --NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
a-RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R' is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group,
[0018] L.sub.1 is selected from a carbon atom, a substituted or
unsubstituted C1 to C30 alkylene group, a substituted or
unsubstituted C6 to C30 cycloalkylene group, a substituted or
unsubstituted C6 to C30 arylene group, or a substituted or
unsubstituted C6 to C30 heteroarylene group, and a C1 to C30
alkylene group, wherein at least one non-adjacent --CH.sub.2--
group may be replaced by --SO.sub.2--, CO, --O--, --S--, --SO--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 alkyl group), or a combination thereof,
[0019] Y.sub.1 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof,
[0020] m is an integer of 1 or more,
[0021] k1 is 0 or an integer of 1 or more,
[0022] k2 is an integer of 1 or more,
[0023] wherein the sum of m and k2 is an integer of 3 or more,
[0024] provided that m does not exceed the valence of Y.sub.1, and
provided that the sum of k1 and k2 does not exceed the valence of
L.sub.1.
[0025] The second monomer may be represented by Chemical Formula
2.
[R.sup.2 .sub.k3L.sub.2 Y.sub.2--(X).sub.n].sub.k4 Chemical Formula
2
[0026] In Chemical Formula 2,
[0027] X is selected from an aliphatic organic group including a
carbon-carbon double bond or a carbon-carbon triple bond, an
aromatic organic group including a carbon-carbon double bond or a
carbon-carbon triple bond, and an alicyclic organic group including
a carbon-carbon double bond or a carbon-carbon triple bond,
[0028] R.sup.2 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R' is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group,
[0029] L.sub.2 is selected from a carbon atom, a substituted or
unsubstituted C1 to C30 alkylene group, a substituted or
unsubstituted C6 to C30 cycloalkylene group, a substituted or
unsubstituted C6 to C30 arylene group, and a substituted or
unsubstituted C3 to C30 heteroarylene group,
[0030] Y.sub.2 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; or a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof,
[0031] n is an integer of 1 or more,
[0032] k3 is an integer of 0 or more,
[0033] k4 is an integer of 1 or more, and
[0034] wherein the sum of n and k4 is an integer of 3 or more,
[0035] provided that n does not exceed the valence of Y.sub.2,
and
[0036] provided that the sum of k3 and k4 does not exceed the
valence of L.sub.2.
[0037] The first monomer of Chemical Formula 1 may include a
monomer of Chemical Formula 1-1.
##STR00001##
[0038] In Chemical Formula 1-1,
[0039] L1' is selected from carbon; a substituted or unsubstituted
C6 to C30 tetravalent arene-derived group; a substituted or
unsubstituted C3 to C30 tetravalent heteroarene-derived group; a
substituted or unsubstituted C3 to C30 tetravalent
cycloalkane-derived group; and a substituted or unsubstituted C3 to
C30 tetravalent heterocycloalkane-derived group,
[0040] each of Y.sub.a to Y.sub.d are independently a single bond;
a substituted or unsubstituted C1 to C30 alkylene group; a
substituted or unsubstituted C2 to C30 alkenylene group; or a
substituted C1 to C30 alkylene group or a C2 to C30 alkenylene
group, wherein at least one --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, imine --NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, or a
combination thereof, and
[0041] R.sub.a to R.sub.d are each independently selected from
R.sup.1 of Chemical Formula 1 or SH, provided that at least two
groups selected from R.sub.a to R.sub.d are SH.
[0042] The first monomer of Chemical Formula 1 may be at least one
selected from trimethylolpropane tris(3-mercaptopropionate) of
Chemical Formula 1-2, pentaerythritol
tetrakis(3-mercaptopropionate) of Chemical Formula 1-3,
pentaerythritol tetrakis(2-mercaptoacetate of Chemical Formula 1-4,
tris[2-(3-mercaptopropinonyloxy)alkyl]isocyanurate of Chemical
Formula 1-5, a compound of Chemical Formula 1-6, a compound of
Chemical Formula 1-7, and a compound of Chemical Formula 1-8.
##STR00002##
[0043] In Chemical Formula 1-5, R is a substituted or unsubstituted
C1 to C10 alkylene.
##STR00003##
[0044] Herein, n is an integer of 1 to 20.
##STR00004##
[0045] Herein, n is an integer of 1 to 20.
##STR00005##
[0046] Herein, n is an integer of 1 to 20.
[0047] In Chemical Formula 2, X is selected from an acrylate group;
a methacrylate group; a C2 to C30 alkenyl group; a C2 to C30
alkynyl group; a substituted or unsubstituted C3 to C30 alicyclic
organic group having a carbon-carbon double bond or a carbon-carbon
triple bond in the ring; a substituted or unsubstituted C3 to C30
heterocycloalkyl group having a carbon-carbon double bond or a
carbon-carbon triple bond in the ring; a C3 to C30 alicyclic
organic group substituted with a C2 to C30 alkenyl group or a C2 to
C30 alkynyl group; and a C3 to C30 heterocycloalkyl group
substituted with a C2 to C30 alkenyl group or a C2 to C30 alkynyl
group.
[0048] The substituted or unsubstituted C3 to C30 alicyclic organic
group having a carbon-carbon double bond or a carbon-carbon triple
bond in the ring may be at least one selected from a norbornene
group, a maleimide group, a nadimide group, and a
tetrahydrophthalimide group.
[0049] The second monomer may be at least one selected from a C4 to
C100 diallyl compound, a C4 to C100 triallyl compound, a C4 to C100
diallyl ether compound, a C4 to C100 triallyl ether compound, a C4
to C100 di(meth)acrylate compound, and a C4 to C100
tri(meth)acrylate compound, a divinyl ether compound.
[0050] In Chemical Formula 2, L.sup.2 may be selected from a group
including a pyrrolidine moiety, a tetrahydrofuran moiety, a
pyridine moiety, a pyrimidine moiety, a piperidine moiety, a
triazine moiety, and an isocyanurate moiety.
[0051] The second monomer of Chemical Formula 2 may be selected
from a compound represented by Chemical Formula 2-1, Chemical
Formula 2-2, and Chemical Formula 2-3.
##STR00006##
[0052] In Chemical Formulae 2-1 and 2-2,
[0053] each of Z.sub.1 to Z.sub.3 independently corresponds to
*--Y.sub.2--X.sub.n as defined in Chemical Formula 2.
##STR00007##
[0054] In Chemical Formula 2-3,
[0055] L.sub.2' is selected from carbon; a substituted or
unsubstituted C1 to C30 tetravalent alkane-derived group; a
substituted or unsubstituted C2 to C30 tetravalent alkene-derived
group; a C1 to C30 tetravalent alkane-derived group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, a C6 to C10 cycloalkylene group, or
a combination thereof; a C2 to C30 tetravalent alkane-derived
group, wherein at least one --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, --NR--, wherein R is hydrogen
or a C1 to C10 linear or branched alkyl group, a C6 to C10
cycloalkylene group, or a combination thereof; a substituted or
unsubstituted C6 to C30 tetravalent arene-derived group; a
substituted or unsubstituted C3 to C30 tetravalent
heteroarene-derived group; a substituted or unsubstituted C3 to C30
tetravalent cycloalkane-derived group; and a substituted or
unsubstituted C3 to C30 tetravalent heterocycloalkane-derived
group,
[0056] each of Y.sub.a to Y.sub.d are independently selected from a
single bond; a substituted or unsubstituted C1 to C30 alkylene
group; a substituted or unsubstituted C2 to C30 alkenylene group;
or a C1 to C30 alkylene group or a C2 to C30 alkenylene group,
wherein at least one --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, --NR--, wherein R is hydrogen
or a C1 to C10 linear or branched alkyl group or a combination
thereof, and
[0057] each of R'.sub.a to R'.sub.d independently corresponds to
R.sup.2 or X of Chemical Formula 2, provided that at least two of
R'.sub.a to R'.sub.d are X of Chemical Formula 2.
[0058] The second monomer may include at least one selected from a
compound of Chemical Formula 2-4, a compound of Chemical Formula
2-5, a compound of Chemical Formula 2-6, a compound of Chemical
Formula 2-7, a compound of Chemical Formula 2-8, a compound of
Chemical Formula 2-9, a compound of Chemical Formula 2-10, a
compound of Chemical Formula 2-11, a compound of Chemical Formula
2-12, a compound of Chemical Formula 2-13, a compound of Chemical
Formula 2-14, and a compound of Chemical Formula 2-15.
##STR00008##
[0059] In Chemical Formula 2-7,
[0060] R.sub.1 is selected from a C1 to C20 alkylene group and a C1
to C20 alkylene group, wherein at least one --CH.sub.2-- group is
replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--,
--S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof,
[0061] and R.sub.2 is selected from hydrogen and a methyl
group.
##STR00009##
[0062] In Chemical Formula 2-8, R is a C1 to C10 alkyl group.
##STR00010##
[0063] In Chemical Formula 2-9,
[0064] A is a C1 to C10 alkyl group or a hydroxy group,
[0065] R.sub.1 is selected from a single bond, a C1 to C20 alkylene
group and a C1 to C20 alkylene, wherein at least one --CH.sub.2--
group is replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--,
--S--, --S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof, and
[0066] R.sub.2 is selected from hydrogen and a methyl group.
##STR00011##
[0067] In Chemical Formula 2-10,
[0068] R.sub.1 is selected from a C1 to C20 alkylene and a C1 to
C20 alkylene, wherein at least --CH.sub.2-- group is replaced by
--S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 linear or branched alkyl group, --NR--, wherein R is hydrogen
or a C1 to C10 linear or branched alkyl group, or a combination
thereof, and
[0069] R.sub.2 is selected from hydrogen and a methyl group.
##STR00012##
[0070] In Chemical Formula 2-11,
[0071] R is selected from a single bond and a C1 to C20 alkylene or
a C1 to C20 alkylene, wherein at least one --CH.sub.2-- group is
replaced by --S(.dbd.O).sub.2--, --C(.dbd.O)--, --O--, --S--,
--S(.dbd.O)--, --C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group, --NR--,
wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group, or a combination thereof.
##STR00013##
[0072] In Chemical Formula 2-12,
[0073] R is a C1 to C20 alkylene, or a C1 to C20 alkylene, wherein
at least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, S--), --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof.
##STR00014##
[0074] The monomer mixture may further include at least one of a
third monomer having one thiol group at its terminal end and a
fourth monomer having one carbon-carbon unsaturated bond-containing
group at its terminal end, or a combination thereof.
[0075] The zinc compound may include at least one selected from a
zinc inorganic acid salt including a counter ion of pKa of at least
3, a zinc organic acid salt, a zinc halide, a zinc oxide, a zinc
metal, and a dialkyl zinc, and
[0076] the indium compound may include at least one selected from
an indium inorganic acid salt including a counter ion of pKa of at
least 3, an indium organic acid salt, an indium halide, an indium
oxide, an indium metal, and a dialkyl indium.
[0077] The composition may include the additive in an amount of
about 10.sup.-6 parts by weight to about 10 parts by weight based
on 100 parts by weight of the monomer mixture.
[0078] The composition may include the light emitting particle in
an amount of about 0.1 to about 20 parts by weight based on 100
parts by weight of the monomer mixture.
[0079] In the monomer mixture, the first monomer and the second
monomer may be present in such an amount that a mole ratio between
the thiol group of the first monomer and the carbon-carbon
unsaturated bond of the second monomer may be about 1:about 0.75 to
about 3, for example, about 1:about 1.1 to about 2, or about
1:about 1.5 to about 1.8.
[0080] In another embodiment, the polymer composite includes:
[0081] a thiol-ene cross-linking polymerization product of a first
monomer having at least two thiol groups at its terminal end and a
second monomer having at least two carbon-carbon unsaturated
bond-containing groups at its terminal end; and
[0082] at least one additive selected from a zinc compound, an
indium compound, ascorbic acid or a salt thereof, citric acid or a
salt thereof, a tocopherol, and a tocotrienol.
[0083] The polymer composite may further include a light emitting
particle selected from a Group II-VI compound semiconductor
nanocrystal, a Group III-V compound semiconductor nanocrystal, a
Group IV-VI compound semiconductor nanocrystal, and a Group IV
compound semiconductor nanocrystal.
[0084] The polymer composite may further include at least one light
emitting particle selected from a metal nanocrystal, a metal oxide
nanocrystal, a phosphor, and a pigment.
[0085] The first monomer may be represented by Chemical Formula
1.
[R.sup.1 .sub.k1L.sub.1 Y.sub.1--(SH).sub.m].sub.k2 Chemical
Formula 1
[0086] In Chemical Formula 1,
[0087] R.sup.1 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; --NH.sub.2; NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R' is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group,
[0088] L.sub.1 is selected from a carbon atom, a substituted or
unsubstituted C1 to C30 alkylene group, a substituted or
unsubstituted C6 to C30 cycloalkylene group, a substituted or
unsubstituted C6 to C30 arylene group, or a substituted or
unsubstituted C6 to C30 heteroarylene group, and a C1 to C30
alkylene group, wherein at least one non-adjacent --CH.sub.2--
group is replaced by --SO.sub.2--, CO, --O--, --S--, --SO--,
--C(.dbd.O)O--, --C(.dbd.O)NR--, wherein R is hydrogen or a C1 to
C10 alkyl group, or a combination thereof,
[0089] Y.sub.1 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof,
[0090] m is an integer of 1 or more,
[0091] k1 is 0 or an integer of 1 or more,
[0092] k2 is an integer of 1 or more,
[0093] wherein the sum of m and k2 is an integer of 3 or more,
[0094] provided that m does not exceed the valence of Y.sub.1, and
provided that the sum of k1 and k2 does not exceed the valence of
L.sub.1.
[0095] The second monomer may be represented by Chemical Formula
2.
[R.sup.2 .sub.k3L.sub.2 Y.sub.2--(X).sub.n].sub.k4 Chemical Formula
2
[0096] In Chemical Formula 2,
[0097] X is selected from an aliphatic organic group including a
carbon-carbon double bond or a carbon-carbon triple bond, an
aromatic organic group including a carbon-carbon double bond or a
carbon-carbon triple bond, and an alicyclic organic group including
a carbon-carbon double bond or a carbon-carbon triple bond,
[0098] R.sup.2 is selected from hydrogen; a substituted or
unsubstituted C1 to C30 linear or branched alkyl group; a
substituted or unsubstituted C6 to C30 aryl group; a substituted or
unsubstituted C7 to C30 arylalkyl group; a substituted or
unsubstituted C3 to C30 heteroaryl group; a substituted or
unsubstituted C4 to C30 heteroarylalkyl group; a substituted or
unsubstituted C3 to C30 cycloalkyl group; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group; a C1 to C10 alkoxy
group; a hydroxy group; NH.sub.2; --NRR', wherein R and R' are
independently hydrogen or a C1 to C30 linear or branched alkyl
group; an isocyanate group; a halogen; --ROR', wherein R is a
substituted or unsubstituted C1 to C20 alkylene group and R' is
hydrogen or a C1 to C20 linear or branched alkyl group;
--RC(.dbd.O)X, wherein R is a substituted or unsubstituted alkylene
group and X is a halogen; --C(.dbd.O)OR', wherein R' is hydrogen or
a C1 to C20 linear or branched alkyl group; --CN; and
--C(.dbd.O)ONRR', wherein R and R' are independently hydrogen or a
C1 to C20 linear or branched alkyl group,
[0099] L.sub.2 is selected from a carbon atom, a substituted or
unsubstituted C1 to C30 alkylene group, a substituted or
unsubstituted C6 to C30 cycloalkylene group, a substituted or
unsubstituted C6 to C30 arylene group, and a substituted or
unsubstituted C3 to C30 heteroarylene group,
[0100] Y.sub.2 is selected from a single bond; a substituted or
unsubstituted C1 to C30 alkylene group; a substituted or
unsubstituted C2 to C30 alkenylene group; and a substituted C1 to
C30 alkylene group or a C2 to C30 alkenylene group, wherein at
least one --CH.sub.2-- group is replaced by --S(.dbd.O).sub.2--,
--C(.dbd.O)--, --O--, --S--, --S(.dbd.O)--, --C(.dbd.O)O--,
--C(.dbd.O)NR--, wherein R is hydrogen or a C1 to C10 linear or
branched alkyl group, --NR--, wherein R is hydrogen or a C1 to C10
linear or branched alkyl group, or a combination thereof,
[0101] n is an integer of 1 or more,
[0102] k3 is an integer of 0 or more,
[0103] k4 is an integer of 1 or more,
[0104] wherein the sum of n and k4 is an integer of 3 or more,
provided that n does not exceed the valence of Y.sub.2, and
provided that the sum of k3 and k4 does not exceed the valence of
L.sub.2.
[0105] The thiol-ene cross-linking polymerization product may be a
polymerization product of a monomer mixture further including at
least one of a third monomer having one thiol group at its terminal
end and a fourth monomer having one carbon-carbon unsaturated
bond-containing group at its terminal end.
[0106] The zinc compound may include at least one selected from a
zinc inorganic acid salt including a counter ion with pKa of at
least 3, a zinc organic acid salt, a zinc halide, a zinc oxide, a
zinc metal, and a dialkyl zinc, and
[0107] the indium compound may include at least one selected from
an indium inorganic acid salt including a counter ion with pKa of
at least 3, an indium organic acid salt, an indium halide, an
indium oxide, an indium metal, and a dialkyl indium.
[0108] Another embodiment provides a film including the polymer
composite.
[0109] The film may further include a barrier film contacting the
surface of the composite.
[0110] In yet another embodiment, an electronic device includes the
film.
[0111] The electronic device may be at least one selected from a
display, a light emitting device, a memory device, a laser device,
and a solar cell.
[0112] The light emitting device may include a light source,
wherein the film is positioned so that the film may transmit light
emitted from the light source.
BRIEF DESCRIPTION OF THE DRAWINGS
[0113] These and/or other aspects will become apparent and more
readily appreciated from the following description of the
embodiments, taken in conjunction with the accompanying drawings in
which:
[0114] FIG. 1 is a diagram showing a polymerization-related
reaction scheme in a thiol-ene system;
[0115] FIG. 2 is a diagram showing an initiation reaction scheme
that may occur during (undesired) curing in the thiol-ene
system;
[0116] FIG. 3 is a graph of luminescence intensity (arbitrary
units, a. u.) versus wavelength (nanometer, nm), showing the result
of Example 4.
[0117] FIG. 4 is a graph of luminescence intensity (arbitrary
units, a. u.) versus wavelength (nanometer, nm), showing the result
of Example 5;
[0118] FIG. 5 schematically shows a liquid crystal display device
including a backlight unit according to an embodiment; and
[0119] FIG. 6 schematically shows a liquid crystal display device
including a backlight unit according to another embodiment.
DETAILED DESCRIPTION
[0120] This disclosure will be described more fully hereinafter in
the following detailed description, in which some but not all
embodiments of this disclosure are described. This disclosure may
be embodied in many different forms and is not be construed as
limited to the embodiments set forth herein; rather, these
embodiments are provided so that this disclosure will fully convey
the scope of the disclosure to those skilled in the art. Thus, in
some exemplary embodiments, well known technologies are not
specifically explained to avoid ambiguous understanding of the
present inventive concept. Accordingly, the exemplary embodiments
are merely described below, by referring to the figures, to explain
aspects of the present inventive concept. Expressions such as "at
least one of," when preceding a list of elements, modify the entire
list of elements and do not modify the individual elements of the
list. Unless otherwise defined, all terms used in the specification
(including technical and scientific terms) may be used with
meanings commonly understood by a person having ordinary knowledge
in the art to which this invention belongs. Further, unless
explicitly defined to the contrary, the terms defined in a
generally-used dictionary should be interpreted as having a meaning
that is consistent with their meaning in the context of the
relevant art and the present disclosure, and are not ideally or
excessively interpreted. In addition, unless explicitly described
to the contrary, the word "comprise" and variations such as
"comprises" or "comprising", and the word "include" and variations
such as "includes" or "including", when used in this specification,
specify the presence of stated features, regions, integers, steps,
operations, elements, and/or components, but do not preclude the
presence or addition of one or more other features, regions,
integers, steps, operations, elements, components, and/or groups
thereof. Therefore, the above words will be understood to imply the
inclusion of stated elements but not the exclusion of any other
elements.
[0121] It will be understood that, although the terms first,
second, third etc. may be used herein to describe various elements,
components, regions, layers, and/or sections, these elements,
components, regions, layers, and/or sections should not be limited
by these terms. These terms are only used to distinguish one
element, component, region, layer, or section from another element,
component, region, layer, or section. Thus, a first element,
component, region, layer, or section discussed below could be
termed a second element, component, region, layer, or section
without departing from the teachings of the present
embodiments.
[0122] The terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting. As
used herein, the singular forms "a," "an," and "the" are intended
to include the plural forms as well, unless the context clearly
indicates otherwise.
[0123] Spatially relative terms, such as "beneath," "below,"
"lower," "above," "upper" and the like, may be used herein for ease
of description to describe one element or feature's relationship to
another element(s) or feature(s) as illustrated in the figures. It
will be understood that the spatially relative terms are intended
to encompass different orientations of the device in use or
operation in addition to the orientation depicted in the figures.
For example, if the device in the figures is turned over, elements
described as "below" or "beneath" other elements or features would
then be oriented "above" the other elements or features. Thus, the
exemplary term "below" can encompass both an orientation of above
and below. The device may be otherwise oriented (rotated 90 degrees
or at other orientations) and the spatially relative descriptors
used herein interpreted accordingly.
[0124] "About" or "approximately" as used herein is inclusive of
the stated value and means within an acceptable range of deviation
for the particular value as determined by one of ordinary skill in
the art, considering the measurement in question and the error
associated with measurement of the particular quantity (i.e., the
limitations of the measurement system).
[0125] Exemplary embodiments are described herein with reference to
cross section illustrations that are schematic illustrations of
idealized embodiments. As such, variations from the shapes of the
illustrations as a result, for example, of manufacturing techniques
and/or tolerances, are to be expected. Thus, embodiments described
herein should not be construed as limited to the particular shapes
of regions as illustrated herein but are to include deviations in
shapes that result, for example, from manufacturing. For example, a
region illustrated or described as flat may, typically, have rough
and/or nonlinear features. Moreover, sharp angles that are
illustrated may be rounded. Thus, the regions illustrated in the
figures are schematic in nature and their shapes are not intended
to illustrate the precise shape of a region and are not intended to
limit the scope of the present claims.
[0126] As stated above, unless specifically described to the
contrary, a singular form includes a plural form.
[0127] In the drawings, the thickness of layers, films, panels,
regions, etc., are exaggerated for clarity. Like reference numerals
designate like elements throughout the specification.
[0128] It will be understood that when an element such as a layer,
film, region, or substrate is referred to as being "on" another
element, it can be directly on the other element or intervening
elements may also be present. In contrast, when an element is
referred to as being "directly on" another element, there are no
intervening elements present.
[0129] As used herein, when a definition is not otherwise provided,
the term "substituted" refers to a compound wherein at least one of
hydrogen atoms thereof is substituted with a substituent selected
from a C1 to C30 alkyl group, a C2 to C30 alkynyl group, a C6 to
C30 aryl group, a C7 to C30 alkylaryl group, a C1 to C30 alkoxy
group, a C1 to C30 heteroalkyl group, a C3 to C30 heteroalkylaryl
group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl
group, a C6 to C30 cycloalkynyl group, a C2 to C30 heterocycloalkyl
group, a halogen (--F, --Cl, --Br, or --I), a hydroxy group (--OH),
a nitro group (--NO.sub.2), a cyano group (--CN), an amino group
(--NRR', wherein R and R' are hydrogen or a C1 to C6 alkyl group),
an azido group (--N.sub.3), an amidino group
(--C(.dbd.NH)NH.sub.2), a hydrazino group (--NHNH.sub.2), a
hydrazono group (.dbd.N(NH.sub.2), an aldehyde group
(--C(.dbd.O)H), a carbamoyl group (--C(O)NH.sub.2), a thiol group
(--SH), an ester group (--C(.dbd.O)OR wherein R is a C1 to C6 alkyl
group or a C6 to C12 aryl group), a carboxyl group (--COOH) or a
salt thereof (--C(.dbd.O)OM, wherein M is an organic or inorganic
cation), a sulfonic acid group (--SO.sub.3H) or a salt thereof
(--SO.sub.3M, wherein M is an organic or inorganic cation), and a
phosphoric acid group (--PO.sub.3H.sub.2) or a salt thereof
(--PO.sub.3MH or --PO.sub.3M.sub.2, wherein M is an organic or
inorganic cation).
[0130] As used herein, the term "monovalent organic functional
group" refers to a C1 to C30 alkyl group, a C2 to C30 alkynyl
group, a C6 to C30 aryl group, a C7 to C30 alkylaryl group, a C1 to
C30 alkoxy group, a C1 to C30 heteroalkyl group, a C3 to C30
heteroalkylaryl group, a C3 to C30 cycloalkyl group, a C3 to C15
cycloalkenyl group, a C6 to C30 cycloalkynyl group, or a C2 to C30
heterocycloalkyl group.
[0131] As used herein, the term "monovalent to trivalent metal
salt" refers to a cation of an alkali metal or an alkaline-earth
metal, or a cation of a transition metal.
[0132] As used herein, the term "hetero" refers to inclusion of one
to three heteroatoms selected from the group consisting of N, O, S,
Si, and P.
[0133] As used herein, the term "alkyl group" may refer to a group
derived from a straight or branched chain saturated aliphatic
hydrocarbon having the specified number of carbon atoms and having
a valence of at least one.
[0134] As used herein, the term "alkoxy group" may refer to
"alkyl-O-", wherein the term "alkyl" has the same meaning as
described above.
[0135] As used herein, the term "alkenyl group" may refer to a
straight or branched chain, monovalent hydrocarbon group having at
least one carbon-carbon double bond.
[0136] As used herein, the term "alkynyl group" may refer to a
straight or branched chain, monovalent hydrocarbon group having at
least one carbon-carbon triple bond.
[0137] As used herein, the term "cycloalkyl group" may refer to a
monovalent group having one or more saturated rings in which all
ring members are carbon.
[0138] As used herein, the term "aryl", which is used alone or in
combination, may refer to an aromatic hydrocarbon containing at
least one ring and having the specified number of carbon atoms. The
term "aryl" may be construed as including a group with an aromatic
ring fused to at least one cycloalkyl ring.
[0139] The term "heteroaryl group" may refer to an aryl group
including carbon and 1 to 3 heteroatoms selected from the group
consisting of N, O, S, and P as ring atoms.
[0140] The term "arylalkyl group" may refer to a substituted or
unsubstituted aryl group covalently linked to an alkyl group that
is linked to a compound.
[0141] The term "heteroarylalkyl group" may refer to a substituted
or unsubstituted heteroaryl group covalently linked to an alkyl
group that is linked to a compound.
[0142] As used herein, the term "alkylene group" may refer to a
straight or branched saturated aliphatic hydrocarbon group having a
valence of at least two, optionally substituted with one or more
substituents where indicated, provided that the valence of the
alkylene group is not exceeded.
[0143] As used herein, the term "alkenylene group" may refer to a
straight or branched aliphatic hydrocarbon group having a valence
of at least two, having at least one carbon-carbon double bond,
optionally substituted with one or more substituents where
indicated, provided that the valence of the alkylene group is not
exceeded.
[0144] As used herein, the term "cycloalkylene group" may refer to
a cyclic hydrocarbon group having a valence of at least two,
optionally substituted with one or more substituents where
indicated, provided that the valence of the cycloalkylene group is
not exceeded.
[0145] As used herein, the term "arylene group" may refer to a
functional group having a valence of at least two obtained by
removal of two hydrogens in an aromatic ring, optionally
substituted with one or more substituents where indicated, provided
that the valence of the alkylene group is not exceeded.
[0146] As used herein, the term "heteroarylene group" may refer to
a functional group having a valence of at least two obtained by
removal of two hydrogens in an aromatic ring, containing one to
three heteroatoms selected from the group consisting of N, O, S,
Si, and P as ring-forming elements, optionally substituted with one
or more substituents where indicated, provided that the valence of
the alkylene group is not exceeded.
[0147] As used herein, the term "aliphatic organic group" refers to
a C1 to C30 linear or branched alkyl group, the term "aromatic
organic group" refers to a C6 to C30 aryl group or a C2 to C30
heteroaryl group, and the term "alicyclic organic group" refers to
a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, or a
C3 to C30 cycloalkynyl group. As used herein, the term
"carbon-carbon unsaturated bond-containing substituent" refers to a
C2 to C20 alkenyl group including at least one carbon-carbon double
bond, a C2 to C20 alkynyl group including at least one
carbon-carbon triple bond, a C4 to C20 cycloalkenyl group including
at least one carbon-carbon double bond in the ring, or a C4 to C20
cycloalkynyl group including at least one carbon-carbon triple bond
in the ring.
[0148] As used herein, the term "(meth)acrylate" refers to acrylate
and/or methacrylate.
[0149] In an embodiment, a composition includes a monomer mixture
of a first monomer having at least two thiol (--SH) groups at its
terminal end and a second monomer having at least two carbon-carbon
unsaturated bond-containing groups at its terminal end; and at
least one an additive selected from a zinc compound, an indium
compound, ascorbic acid or a salt thereof, citric acid or a salt
thereof, a tocopherol, and a tocotrienol.
[0150] The first monomer may be represented by the following
Chemical Formula 1.
[R.sup.1 .sub.k1L.sub.1 Y.sub.1--(SH).sub.m].sub.k2 Chemical
Formula 1
[0151] In Chemical Formula 1, the definitions of R.sup.1, L.sub.1,
Y.sub.1, m, k1, and k2 are the same as set forth above.
[0152] The first monomer of Chemical Formula 1 may include a
monomer of the following Chemical Formula 1-1.
##STR00015##
[0153] In Chemical Formula 1-1, the definitions of L.sub.1',
Y.sub.a to Y.sub.d, and R.sub.a to R.sub.d are the same as set
forth above.
[0154] For example, the first monomer of Chemical Formula 1 may be
at least one selected from trimethylolpropane
tris(3-mercaptopropionate) of the following Chemical Formula 1-2,
pentaerythritol tetrakis(3-mercaptopropionate) of the following
Chemical Formula 1-3, pentaerythritol tetrakis(2-mercaptoacetate)
of the following Chemical Formula 1-4,
tris[2-(3-mercaptopropionyloxyl)alkyl]isocyanurate of the following
Chemical Formula 1-5, pentaerythritol tetrakis(3-mercaptobutylate,
trimethylolpropane tris(3-mercaptopropionate) (3T),
tris[2-(3-mercaptopropinonyloxy)ethyl]isocyanurate (3TI), a
compound of the following Chemical Formula 1-6, a compound of the
following Chemical Formula 1-7, and a compound of the following
Chemical Formula 1-8, but is not limited thereto.
##STR00016##
[0155] In Chemical Formula 1-5, R is a substituted or unsubstituted
C1 to C10 alkylene.
##STR00017##
[0156] Herein, n is an integer of 1 to 20.
##STR00018##
[0157] Herein, n is an integer of 1 to 20.
##STR00019##
[0158] Herein, n is an integer of 1 to 20.
[0159] The compounds of Chemical Formula 1-2 to Chemical Formula
1-8 may be, for example, commercially available from a vendor, for
example from Sartomer, or may be synthesized using a well-known
method.
[0160] The second monomer may be represented by the following
Chemical Formula 2.
[R.sup.2 .sub.k3L.sub.2 Y.sub.2--(X).sub.n].sub.k4 Chemical Formula
2
[0161] In Chemical Formula 2, X, the definitions of R.sup.2,
L.sub.2, Y.sub.2, n, k3, and k4 are the same as set forth
above.
[0162] In an embodiment, X of Chemical Formula 2 may be selected
from an acrylate group; a methacrylate group; a C2 to C30 alkenyl
group; a C2 to C30 alkynyl group; a substituted or unsubstituted C3
to C30 alicyclic organic group having a carbon-carbon double bond
or a carbon-carbon triple bond in the ring; a substituted or
unsubstituted C3 to C30 heterocycloalkyl group having a
carbon-carbon double bond or a carbon-carbon triple bond in the
ring; a C3 to C30 alicyclic organic group substituted with a C2 to
C30 alkenyl group or a C2 to C30 alkynyl group; and a C3 to C30
heterocycloalkyl group substituted with a C2 to C30 alkenyl group
or a C2 to C30 alkynyl group.
[0163] In Chemical Formula 2, L.sup.2 may include one selected from
a linear or branched C1 to C30 alkylene moiety, a tricyclodecane
moiety, a pyrrolidine moiety, a tetrahydrofuran moiety, a pyridine
moiety, a pyrimidine moiety, a piperidine moiety, a triazine
moiety, and an isocyanurate moiety.
[0164] The substituted or unsubstituted C3 to C30 alicyclic organic
group having a carbon-carbon double bond or a carbon-carbon triple
bond in the ring may be at least one selected from a norbornene
group, a maleimide group, a nadimide group, and a
tetrahydrophthalimide group.
[0165] In an embodiment, the second monomer may be at least one
selected from a C4 to C100 diallyl compound such as 1,3-butadiene,
or diallyl succinate, a C7 to C100 triallyl compound such as
triallyl borate, 2,4,6-triallyloxy-1,3,5-triazine, or
1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, a C6 to C100
diallyl ether compound such as allyl ether, trimethylolpropane
diallyl ether, or 2,2'-diallyl bisphenol A diacetate ether, a C10
to C100 triallyl ether compound such as
1-(allyloxy)-2,2-bis((allyloxy)methyl)butane, a C4 to C100
di(meth)acrylate compound such as ethylene glycol dimethacrylate,
hexanediol diacrylate, tricyclodecane dimethanol diacrylate, a C9
to C100 tri(meth)acrylate compound such as trimethylol propane
triacrylate, or ethoxylated trimethylolpropane triacrylate, and a
divinyl ether compound such as triethylene glycol divinyl ether,
bis[4-(vinyloxy)butyl]adipate, or 1,4-butanediol divinyl ether.
[0166] The second monomer of Chemical Formula 2 may be represented
by one selected from Chemical Formula 2-1, Chemical Formula 2-2,
Chemical Formula 2-3, and Chemical Formula 2-4.
##STR00020##
[0167] In Chemical Formulae 2-1 and 2-2, each of Z.sub.1 to Z.sub.3
corresponds independently *--Y.sub.2--X.sub.n as defined for
Chemical Formula 2.
##STR00021##
[0168] In Chemical Formula 2-3,
[0169] L.sub.2' is selected from carbon; a substituted or
unsubstituted C1 to C30 tetravalent alkane-derived group; a
substituted or unsubstituted C2 to C30 tetravalent alkene-derived
group; a C1 to C30 tetravalent alkyne-derived group, wherein at
least one methylene (--CH.sub.2--) group is replaced by sulfonyl
(--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether (--O--),
sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester (--C(.dbd.O)O--),
amide (--C(.dbd.O)NR--) (wherein R is hydrogen or a C1 to C10
linear or branched alkyl group), imine (--NR--) (wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), a C6 to
C10 cycloalkylene group, or a combination thereof; a C2 to C30
tetravalent alkene-derived group, wherein at least one methylene
(--CH.sub.2--) group is replaced by sulfonyl (--S(.dbd.O).sub.2--),
carbonyl (--C(.dbd.O)--), ether (--O--), sulfide (--S--), sulfoxide
(--S(.dbd.O)--), ester (--C(.dbd.O)O--), amide (--C(.dbd.O)NR--)
(wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group), imine (--NR--) (wherein R is hydrogen or a C1 to C10 linear
or branched alkyl group), a C6 to C10 cycloalkylene group, or a
combination thereof; a substituted or unsubstituted C6 to C30
tetravalent arene-derived group; a substituted or unsubstituted C3
to C30 tetravalent heteroarene-derived group; a substituted or
unsubstituted C3 to C30 tetravalent cycloalkane-derived group; and
a substituted or unsubstituted C3 to C30 tetravalent
heterocycloalkane-derived group,
[0170] each of Y.sub.a to Y.sub.d are independently selected from a
single bond; a substituted or unsubstituted C1 to C30 alkylene
group; a substituted or unsubstituted C2 to C30 alkenylene group;
or a C1 to C30 alkylene group or a C2 to C30 alkenylene group,
wherein at least one methylene (--CH.sub.2--) group is replaced by
sulfonyl (--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether
(--O--), sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester
(--C(.dbd.O)O--), amide (--C(.dbd.O)NR--) (wherein R is hydrogen or
a C1 to C10 linear or branched alkyl group), imine (--NR--)
(wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group), or a combination thereof, and
[0171] R'.sub.a to R'.sub.d are R.sup.2 or X of Chemical Formula 2,
provided that at least two of R'.sub.a to R'.sub.d are X of
Chemical Formula 2.
[0172] In an embodiment, the second monomer may include at least
one selected from a compound of the following Chemical Formula 2-4,
a compound of the following Chemical Formula 2-5, a compound of the
following Chemical Formula 2-6, a compound of the following
Chemical Formula 2-7, a compound of the following Chemical Formula
2-8, a compound of the following Chemical Formula 2-9, a compound
of the following Chemical Formula 2-10, a compound of the following
Chemical Formula 2-11, a compound of the following Chemical Formula
2-12, a compound of the following Chemical Formula 2-13, a compound
of the following Chemical Formula 2-14, and a compound of the
following Chemical Formula 2-15.
##STR00022##
[0173] In Chemical Formula 2-7, R.sub.1 is selected from a C1 to
C20 alkylene group and a C1 to C20 alkylene group, wherein at least
one methylene (--CH.sub.2--) group is replaced by sulfonyl
(--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether (--O--),
sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester (--C(.dbd.O)O--),
amide (--C(.dbd.O)NR--) (wherein R is hydrogen or a C1 to C10
linear or branched alkyl group), imine (--NR--) (wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), or a
combination thereof, and R.sub.2 is selected from hydrogen and a
methyl group.
##STR00023##
[0174] In Chemical Formula 2-8, R is a C1 to C10 alkyl group.
##STR00024##
[0175] In Chemical Formula 2-9, A is selected from a C1 to C10
alkyl group and a hydroxy group; R.sub.1 is selected from a single
bond, a C1 to C20 alkylene group and a C1 to C20 alkylene, wherein
at least one methylene (--CH.sub.2--) group is replaced by sulfonyl
(--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether (--O--),
sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester (--C(.dbd.O)O--),
amide (--C(.dbd.O)NR--) (wherein R is hydrogen or a C1 to C10
linear or branched alkyl group), imine (--NR--) (wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), or a
combination thereof, and R.sub.2 is selected from hydrogen and
methyl group.
##STR00025##
[0176] In Chemical Formula 2-10, R.sub.1 is selected from a C1 to
C20 alkylene and a C1 to C20 alkylene, wherein at least one
methylene (--CH.sub.2--) group is replaced by sulfonyl
(--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether (--O--),
sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester (--C(.dbd.O)O--),
amide (--C(.dbd.O)NR--) (wherein R is hydrogen or a C1 to C10
linear or branched alkyl group), imine (--NR--) (wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), or a
combination thereof, and R.sub.2 is selected from hydrogen and
methyl group.
##STR00026##
[0177] In Chemical Formula 2-11, R is selected from a single bond,
a C1 to C20 alkylene, and a C1 to C20 alkylene, wherein at least
one methylene (--CH.sub.2--) group is replaced by sulfonyl
(--S(.dbd.O).sub.2--), carbonyl (--C(.dbd.O)--), ether (--O--),
sulfide (--S--), sulfoxide (--S(.dbd.O)--), ester (--C(.dbd.O)O--),
amide (--C(.dbd.O)NR--) (wherein R is hydrogen or a C1 to C10
linear or branched alkyl group), imine (--NR--) (wherein R is
hydrogen or a C1 to C10 linear or branched alkyl group), or a
combination thereof.
##STR00027##
[0178] In Chemical Formula 2-12, R is selected from a C1 to C20
alkylene and a C1 to C20 alkylene, wherein at least one methylene
(--CH.sub.2--) group is replaced by sulfonyl (--S(.dbd.O).sub.2--),
carbonyl (--C(.dbd.O)--), ether (--O--), sulfide (--S--), sulfoxide
(--S(.dbd.O)--), ester (--C(.dbd.O)O--), amide (--C(.dbd.O)NR--)
(wherein R is hydrogen or a C1 to C10 linear or branched alkyl
group), imine (--NR--) (wherein R is hydrogen or a C1 to C10 linear
or branched alkyl group), or a combination thereof.
##STR00028##
[0179] In the monomer mixture, the amounts of the first monomer and
the second monomer are not particularly limited, and may be
adjusted in order to obtain desired properties. For example, in the
monomer mixture, the amounts of the first monomer and the second
monomer may be adjusted so that a mole ratio between the thiol
group of the first monomer and the carbon-carbon unsaturated bond
of the second monomer may be about 1:0.1 to about 1:10, for
example, about 1:0.2 to about 1:5, about 1:0.75 to about 1:3, about
1:about 1.1 to 2, or about 1:about 1.5 to 1.8. When the monomer
mixture includes the first monomer and the second monomer within
the aforementioned ranges, the prepared polymer composite may form
a high density network, and thus have enhanced mechanical strength
and other properties.
[0180] The composition for the light emitting particle-polymer
composite may further include at least one of a third monomer
having one thiol (--SH) group at its terminal end and a fourth
monomer having one carbon-carbon unsaturated bond-containing group
at its end, or a combination thereof. The third monomer is a
compound where in Chemical Formula 1, m and k2 are 1, and the
fourth monomer is a compound where in Chemical Formula 2, n and k4
are 1.
[0181] Examples of the third monomer may be a C1 to C20 alkyl
3-mercaptopropionate, alkylthio glycolate, a C1 to C20 thiol
substituted (meth)acrylate, a C1 to C20 thiol substituted silane,
for example (3-mercaptopropyl)trimethoxysilane, but are not limited
thereto.
[0182] Examples of the fourth monomer may include (meth)acrylates
such as isobornyl (meth)acrylate, isooctyl (meth)acrylate, lauryl
(meth)acrylate, benzoyl (meth)acrylate, norbornyl acrylate,
(meth)acrylate, cyclohexyl (meth)acrylate, n-hexyl (meth)acrylate,
iso-octyl (meth)acrylate, butyl (meth)acrylate, adamantyl acrylate,
or cyclopentyl acrylate; alkenes such as vinyl ether, alkyl ether,
propenyl ether, pentene, or hexyne; unsaturated ester, maleimide,
acrylonitrile, styrene, diene, or N vinyl amide, but are not
limited thereto.
[0183] The amounts of the third monomer and the fourth monomer are
not particularly limited, and may be selected on the basis of
miscibility, viscosity, release properties, and optical properties.
For example, the amount of the third monomer such as
(3-mercaptopropyl)trimethoxysilane may be about 30 parts by weight
or less, for example about 20 parts by weight or less, about 15
parts by weight or less, or about 10 parts by weight or less based
on 100 parts by weight of the monomer mixture, and the amount of
the fourth monomer such as lauryl methacrylate may be about 30
parts by weight or less, for example, about 20 parts by weight or
less, about 15 parts by weight or less, about 12 parts by weight or
less, or about 10 parts by weight or less based on 100 parts by
weight of the monomer mixture, but are not limited thereto. Within
the above ranges, the prepared composite may have improved
mechanical properties, and a process of manufacturing a composite
may be performed smoothly.
[0184] The di(meth)acrylate compound, the tri(meth)acrylate
compound, or the monoacrylate compound may be a polymerizable
oligomer selected from urethane (meth)acrylate, epoxy
(meth)acrylate, polyester (meth)acrylate, acrylic (meth)acrylate,
polybutadiene (meth)acrylate, silicone (meth)acrylate, melamine
(meth)acrylate, and a combination thereof. A molecular weight of
the polymerizable oligomer is not particularly limited, and may be
selected appropriately. For example, a molecular weight of the
polymerizable oligomer may be about 1,000 to about 20,000 grams per
mole (g/mol), but is not limited thereof. Such a polymerizable
oligomer may be synthesized by a well-known method or may be
commercially available.
[0185] The monomer mixture (i.e., thiol-ene system) may provide a
cross-linked polymer by UV irradiation, for example, according to a
reaction scheme shown in FIG. 1. The properties (e.g.,
cross-linking degree) of the polymer prepared from the composition
may be controlled by adjusting the number of the thiol groups of
the first monomer and the number of the unsaturated bonds of the
second monomer.
[0186] The monomer mixture may further include an initiator for
promoting a cross-linking reaction between the thiol group and the
carbon-carbon unsaturated bond. Examples of the initiator may
include a phosphine oxide compound, .alpha.-amino ketone, phenyl
glyoxylate, monoacyl phosphine, benzyldimethyl-ketal,
hydroxyketone, azobisisobutyronitrile (AIBN), benzoyl peroxide, and
the like.
[0187] The polymer prepared from the monomer composition has
improved compatibility with the light emitting particles and may be
cured at room temperature within a short period of time.
Accordingly, the obtained light emitting particles may have
improved light emitting characteristics, and a high temperature
process having an unfavorable influence on the light emitting
particles (e.g., deterioration of stability) may not be needed. In
addition, the prepared polymer composite forms a densely
cross-linked structure and thus prevents oxygen or moisture from
penetrating the composite. Accordingly, the above monomer mixture
and the cross-linked polymer prepared therefrom may stably maintain
optical characteristics of the light emitting particles and be
applied in various fields. For example, the above monomer mixture
and the cross-linking polymer formed therefrom may be usefully
applied to an organic light emitting diode (OLED) such as a light
emitting diode (LED) device or a light emitting device, a memory
device, a laser device, and a photoelectric device such as a solar
cell.
[0188] In particular, research on a QD film using a quantum dot as
a light emitting particle in a display device such as an LCD has
been actively conducted to improve color reproducibility and
display quality. Processes for preparing the QD film are known in
the art. In a process embodiment, the QD film is manufactured by
adding a quantum dot (or a quantum dot dispersion) to a desired
host matrix (i.e., a monomer mixture) and coating the mixture on a
substrate (e.g., by spin-coating, blade-coating, and the like). On
the QD film thus prepared, a filling resin layer may be further
formed by coating the resin or a different monomer or polymer
composition.
[0189] When applied to the QD film, the monomer mixture (i.e., a
thiol-ene system) has many advantages as described above. However,
its poor storage-stability often poses a significant obstacle in a
manufacturing process. In other words, the monomer mixture may
undergo spontaneous initiation during its storage, and thus may
change its initially fluid state to a gel or solid state. This may
pose a serious problem of hampering the formation of a uniform
coating. Without wishing to be bound to any theory, it is believed
that the thiol-ene system may easily undergo self-polymerization
even with a trace amount of a reactive radical present (e.g., a
radical produced by active oxygen in the air) and thus may show
very poor storage stability. For example, as shown in FIG. 3, a
hydroxy radical produced by active oxygen may remove hydrogen from
the double bond carbon or the thiol, producing a propagational
radical and thereby resulting in the initiation of polymerization.
In particular, when a thiol-ene resin is used as a quantum
dot-polymer composite, reactants used during the QD synthesis, for
example, trioctylphosphine, sulfur (S)-coordinated
trioctylphosphine, and the like, are not removed but remain on the
quantum dot, and may further promote the curing of a thiol-ene
system during manufacture of the quantum dot-polymer composite.
[0190] Surprisingly, the present inventors have found that
undesired curing phenomena may be substantially suppressed or
prevented by adding at least one additive selected from a zinc
compound, an indium compound, ascorbic acid or a salt thereof,
citric acid, a citrate salt, a tocopherol, a tocotrienol, and a
combination thereof to the monomer mixture. As used herein, the
term "undesired or natural curing" refers to the embodiment wherein
a monomer composition (i.e., the thiol-ene system) shows a
viscosity increase of greater than or equal to 50% without any
irradiation by UV rays. The aforementioned additive may deactivate
unremoved reactant that may induce a curing of the thiol-ene
system, thus preventing the curing thereof. In addition, the
aforementioned additive may stop propagation of a naturally
occurring, highly reactive radical, thereby enhancing storage
stability of the thiol-ene system. In addition, the aforementioned
additive does not adversely affect the formation of the polymer
composite by the UV curing of the monomer mixture (i.e., the
thiol-ene system). Furthermore, the above additive does not have
any substantial effect on physical or optical properties of a
manufactured film. For example, when the monomer mixture includes
light emitting particles such as quantum dots, the additive
substantially does not really have any substantial effect on the
luminous efficiency and a wavelength of emitted light emitting
particles and their stability in a composition or a polymer
composite.
[0191] Among the additive, the zinc compound may include at least
one selected from a zinc inorganic acid salt or a zinc organic acid
salt including a counter ion with pKa of at least 3, a zinc halide,
a zinc oxide, a zinc metal, and a dialkyl zinc.
[0192] The indium compound may include at least one selected from
an indium inorganic acid salt or an indium organic acid salt
including a counter ion with pKa of at least 3, an indium halide,
an indium oxide, an indium metal, a dialkyl indium, or a
combination thereof. As used herein, the term "organic acid" refers
to a compound represented by a chemical formula of RCOOH (wherein R
is a C1 to C20 alkyl). For example, the zinc inorganic acid salt or
zinc organic acid salt including a counter ion with pKa of at least
3 may be zinc acetate, zinc stearate, zinc oleate, or zinc
palmitate. The zinc halide may include ZnF.sub.2 but does not
include ZnCl.sub.2. The zinc oxide may include ZnO. The dialkyl
zinc may include dimethyl zinc or diethyl zinc. The indium
inorganic acid salt or indium organic acid salt including a counter
ion with pKa of at least 3 may be indium acetate, indium stearate,
indium oleate, or indium palmitate. The indium halide may include
InF.sub.3. The zinc oxide may include In.sub.2O.sub.3. The dialkyl
indium may include dimethyl indium or diethyl indium.
[0193] The additive may be included in an amount of about 0.001
part by weight to about 10 parts by weight, for example, about
0.005 parts by weight to about 1 part by weight, or about 0.01 part
by weight to about 0.1 part by weight based on 100 parts by weight
of the monomer mixture. The amounts within the above range are
desirable in terms of solubility of the additive in the resin
composition.
[0194] The composition may further include at least one light
emitting particle selected from a Group II-VI compound
semiconductor nanocrystal, a Group III-V compound semiconductor
nanocrystal, a Group IV-VI compound semiconductor nanocrystal, and
a Group IV compound semiconductor nanocrystal. The composition may
further include at least one light emitting particle selected from
a metal nanocrystal, a metal oxide nanocrystal, a phosphor, and a
pigment.
[0195] The Group II-IV compound may be selected from a binary
element compound selected from CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO,
HgS, HgSe, HgTe, MgSe, MgS, and a mixture thereof; a ternary
element compound selected from CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe,
ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe,
CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, and a mixture
thereof; and a quaternary element compound selected from HgZnTeS,
CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS,
HgZnSeTe, HgZnSTe, and a mixture thereof.
[0196] The Group III-V compound may be selected from a binary
element compound selected from GaN, GaP, GaAs, GaSb, AlN, AlP,
AlAs, AlSb, InN, InP, InAs, InSb, and a mixture thereof; a ternary
element compound selected from GaNP, GaNAs, GaNSb, GaPAs, GaPSb,
AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb,
and a mixture thereof; and a quaternary element compound selected
from GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs,
GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs,
InAlPSb, and a mixture thereof.
[0197] The Group IV-VI compound may be selected from a binary
element compound selected from SnS, SnSe, SnTe, PbS, PbSe, PbTe,
and a mixture thereof; a ternary element compound selected from
SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe,
and a mixture thereof; and a quaternary element compound selected
from SnPbSSe, SnPbSeTe, SnPbSTe, and a mixture thereof.
[0198] The Group IV compound may be selected from a single-element
compound selected from Si, Ge, and a mixture thereof; and a binary
element compound selected from SiC, SiGe, and a mixture
thereof.
[0199] The binary element compound, the ternary element compound or
the quaternary element compound respectively exist in a uniform
concentration within the semiconductor nanocrystal particle or
partially different concentrations within the same particle. In
addition, the semiconductor nanocrystal may have a core-shell
structure wherein a semiconductor nanocrystal surrounds another
(different) semiconductor nanocrystal. The core and shell may have
an interface, and an element of at least one of the core or the
shell in the interface may have a concentration gradient wherein
the concentration of the element(s) of the shell decreases toward
the core. In addition, the semiconductor nanocrystal may have one
core of a semiconductor nanocrystal and multi-shells surrounding
the core. The core and multi-shell structure has at least two
shells wherein each shell may be a single composition, an alloy, or
the one having a concentration gradient.
[0200] In the semiconductor nanocrystal particle, the materials of
the shell may have a larger energy bandgap than that of the core.
As a result, the semiconductor nanocrystal may exhibit a quantum
confinement effect more effectively. In case of a multi-shell type
of semiconductor nanocrystal particle, the bandgap of the material
of an outer shell may be of higher energy than that of the material
of an inner shell (a shell that is closer to the core). In this
embodiment, the semiconductor nanocrystal may emit light of a
wavelength ranging from UV to infrared light.
[0201] The semiconductor nanocrystal may have quantum efficiency of
greater than or equal to about 10%, greater than or equal to about
30%, for example, greater than or equal to about 50%, greater than
or equal to about 60%, greater than or equal to about 70%, or
greater than or equal to about 90%.
[0202] The semiconductor nanocrystal may be designed to have a
wider or narrower full width at half maximum (FWHM) in its
photoluminescence spectrum depending on its application. By way of
an example, for use in display devices, the semiconductor
nanocrystal may have a narrower FWHM so as to realize enhanced
color purity or color reproducibility. The semiconductor
nanocrystal may have a FWHM of less than or equal to about 45
nanometers (nm), for example less than or equal to about 40 nm, or
less than or equal to about 30 nm. Within such ranges, a device
including the nanocrystal may have enhanced color purity or
improved color reproducibility.
[0203] The semiconductor nanocrystal may have a particle diameter
(the longest diameter in case of a non-spherical particle) ranging
from about 1 nm to about 100 nm, for example about 1 nm to about 20
nm, or for example about 1 nm to 10 nm.
[0204] The shape of the semiconductor nanocrystal is not
particularly limited. By way of an example, the nanocrystal may
have a spherical shape, a pyramidal shape, a multi-arm shape, a
cubic shape, an elliptical shape, a tetrahedral shape, an
octahedral shape, a cylindrical shape, a polygonal pillar-like
shape, a conical shape, a columnar shape, a tubular shape, a
helical shape, a funnel shape, a dendritic shape, or any of various
common regular and irregular shapes. The nanocrystal may be in the
form of a nanoparticle, a nanotube, a nanowire, a nano-fiber, a
nano-plate particle, a nanosheet, or the like.
[0205] The semiconductor nanocrystal may be prepared in any method.
For example, the semiconductor nanocrystal may be prepared by the
method described hereinbelow, but it is not limited thereto.
[0206] In a non-limiting example, the semiconductor nanocrystal
having a several nanometer size may be prepared via a wet chemical
method. In the wet chemical method, precursors react in an organic
solvent to grow nanocrystal particles, and the organic solvent or a
ligand compound may coordinate the surface of the semiconductor
nanocrystal, controlling the growth of the nanocrystal. As the
organic materials on the surface of the semiconductor nanocrystal
may adversely affect the stability of the device, extra organic
materials--not coordinating the surface of the nanocrystal may be
removed by adding the nanocrystal to an excess amount of a
non-solvent and centrifuging the resulting mixture. Examples of the
non-solvent may include, but are not limited to, acetone, ethanol,
and methanol. After the removal of extra organic materials, the
amount of the organic materials coordinated on the surface of the
nanocrystal may be less than or equal to about 35% by weight, based
on the total weight of the nanocrystal. The organic materials may
include a ligand compound, an organic solvent, or a combination
thereof. The ligand compound may be any organic compound that may
be used as a ligand compound in the wet chemical method, and the
types thereof are not particularly limited. For example, the ligand
compound may be RCOOH, RNH.sub.2, R.sub.2NH, R.sub.3N, RSH,
R.sub.3PO, R.sub.3P, ROH, RCOOR', RCONH.sub.2, RCONHR', RCONR'R'',
RCN, RPO(OH).sub.2, or R.sub.2POOH, wherein R and R' are each
independently a C1 to C24 alkyl group, a C2 to C24 alkenyl group,
or a C6 to C24 aryl group. The organic ligand compound may be
coordinated to the surface of the nanocrystals as prepared, to
assist efficient dispersing of the nanocrystals in a solution, and
improving the light-emitting and electrical characteristics of the
nanocrystals. Examples of the organic ligand compound may include,
but are not limited to: a thiol such as methanethiol, ethanethiol,
propanethiol, butanethiol, pentanethiol, hexanethiol, octanethiol,
dodecanethiol, hexadecanethiol, octadecanethiol, and benzylthiol;
an amine such as methaneamine, ethaneamine, propaneamine,
butaneamine, pentaneamine, hexaneamine, octaneamine, dodecaneamine,
hexadecylamine, octadecylamine, dimethylamine, diethylamine,
trioctyl amine, and dipropylamine; an alcohol such as methanol,
ethanol, propanol, and butanol; an acid such as methanoic acid,
ethanoic acid, propanoic acid, butanoic acid, pentanoic acid,
hexanoic acid, heptanoic acid, octanoic acid, dodecanoic acid,
hexadecanoic acid, octadecanoic acid, oleic acid, and benzoic acid;
an ester thereof such as methyl acetate, ethyl acetate, methyl
propionate, ethyl propionate; an amide thereof such as methyl
acetamide, ethyl acetamide, methyl, propionamide, or ethyl
propionamide; a nitrile thereof such as acetonitrile,
propionitrile, butyronitrile; a phosphine such as methylphosphine,
ethylphosphine, propylphosphine, butylphosphine, pentylphosphine,
and the like, or an oxide compound thereof such as methylphosphine
oxide, ethylphosphine oxide, propylphosphine oxide, butylphosphine
oxide, and the like; a diphenylphosphine compound, a
triphenylphosphine compound, and an oxide compound thereof; and a
phosphonic acid. The organic ligand compound may be used alone or
as a mixture of two or more compounds. The solvent may be any one
used in the wet chemical method, and the types thereof are not
particularly limited. For example, the solvent may be selected from
the group consisting of: a C6 to C22 primary amine such as
hexadecylamine, a C6 to C22 secondary amine such as dioctylamine,
and a C6 to C40 tertiary amine such as trioctylamine; a
heterocyclic compound having a nitrogen atom such as pyridine; a C6
to C40 aliphatic hydrocarbon (e.g., alkane, alkene, alkyne, and the
like) such as hexadecane, octadecane, octadecene, and squalane; a
C6 to C40 aromatic hydrocarbon such as phenyl dodecane, phenyl
tetradecane, phenyl hexadecane, and the like; a phosphine
substituted with a C6 to C22 alkyl group such as trioctylphosphine;
a phosphine oxide substituted with a C6 to C22 alkyl group such as
trioctylphosphine oxide; a C12 to C22 aromatic ether such as phenyl
ether, benzyl ether, and the like; and a combination thereof, but
it is not limited thereto.
[0207] In another embodiment, the polymer composite may include a
thiol-ene cross-linking polymerization product of a first monomer
having at least two thiol (--SH) groups at its terminal end and a
second monomer having at least two carbon-carbon unsaturated
bond-containing groups at its end; and at least one an additive
selected from a zinc compound, an indium compound, ascorbic acid or
a salt thereof, citric acid or a salt thereof, a tocopherol, and a
tocotrienol.
[0208] The polymer composite may further include at least one light
emitting particle selected from a Group II-VI compound
semiconductor nanocrystal, a Group III-V compound semiconductor
nanocrystal, a Group IV-VI compound semiconductor nanocrystal, and
a Group IV compound semiconductor nanocrystal.
[0209] The polymer composite may further include at least one light
emitting particle selected from a metal nanocrystal, a metal oxide
nanocrystal, a phosphor, and a pigment.
[0210] The polymer composite may be prepared by polymerizing the
composition (e.g., via heat treatment or UV irradiation), for
example, according to a reaction scheme in FIG. 1. The reaction
scheme of thiol-ene polymerization is known in the art (see J.
Polymer Sci.: Part A: Polymer Chem. Vol. 42, 5301 2004). The first
monomer, the second monomer, the additive, and the light emitting
particle are the same as set forth above.
[0211] In a non-limiting embodiment, the polymer composite may be
prepared by mixing the monomer mixture and the additive, (and then,
if necessary, removing a solvent therefrom) to obtain a
composition, and curing (e.g., UV-curing) the same. During the UV
curing, UV rays may have a wavelength of about 365 nm or less and
at a dose of about 50 milliJoules per square centimeter
(mJ/cm.sup.2) or more, without limitation.
[0212] When the polymer composite includes light emitting
particles, for example, semiconductor nanocrystals (hereinafter,
quantum dots or QD), the polymer composite may be prepared by
removing an excessive organic material from QDs as synthesized in a
colloid state. This can be accomplished by either dispersing the
resultant in an organic solvent or preparing the resultant as a
powder, mixing the resultant with the monomer mixture and the
additive to obtain a composition (if necessary, by removing the
solvent), and curing the composition (e.g., by UV-curing). Examples
of the organic solvent for dispersion may include, but are not
limited to, chloroform, hexene, an acrylate-based monomer, or a
combination thereof. Alternatively, after substituting the surface
of the QDs as synthesized in a colloidal state with a polymer
having a similar chemical structure to that of a ligand compound
used during the synthesis thereof, a stable QD-polymer composite
may be formed using the above method.
[0213] In non-limiting examples, various protective films (e.g., a
barrier layer) such as a silica, titania, or alumina film for
blocking oxygen or moisture may be disposed (e.g., coated or
laminated) on the semiconductor nanocrystal-polymer composite so as
to enhance the stability of the composite.
[0214] Another embodiment provides a film including the polymer
composite. The film may further include a barrier film contacting
the surface of the composite. Non-limiting examples of a method of
manufacturing such a film are the same as in the method of
manufacturing the QD film which is described above in detail.
[0215] In another embodiment, an electronic device includes the
film.
[0216] The electronic device may be a display, a light emitting
device such as a backlight unit for a liquid crystal display
device, a memory device, a laser device, or a solar cell.
[0217] The light emitting device may include a light source, and
the film is positioned in such a way that the film may transmit
light emitted from the light source.
[0218] The device may be manufactured according to known methods,
and a specific structure thereof is also known in the art. As a
non-limiting example, a backlight unit for a liquid crystal display
device is described in detail as follows.
[0219] The backlight unit includes an LED light source;
[0220] a light conversion layer disposed separately from the LED
light source to convert light emitted from the LED light source to
white light and to provide the white light to the liquid crystal
panel; and
[0221] a light guide panel disposed between the LED light source
and the light conversion layer,
[0222] wherein the light conversion layer includes the
semiconductor nanocrystal-polymer composite. The semiconductor
nanocrystal-polymer composite is the same as set forth above.
Hereinafter, a backlight unit according to an embodiment and a
liquid crystal display device including the same are explained
referring to the drawings.
[0223] FIG. 5 is a schematic view of a liquid crystal display
device 10 including a backlight unit in accordance with an
embodiment.
[0224] Referring to FIG. 5, the liquid crystal display device 10
includes a backlight unit 100 and a liquid crystal panel 500 to
provide a predetermined colored image using white light provided
from the backlight unit 100.
[0225] The backlight unit 100 includes a light emitting diode
("LED") light source 110, a light conversion layer 130 to convert
light emitted from the LED light source 110 to white light, and a
light guide panel 120 disposed therebetween to guide the light
emitted from the LED light source 110 to the light conversion layer
130. The LED light source 110 includes a plurality of LED chips
emitting light having predetermined wavelengths. The LED light
source 110 may be a blue light-emitting LED light source or an
ultraviolet (UV)-emitting LED light source, for example.
[0226] A reflector (not shown) may be further disposed on the lower
surface of the light guide panel 120.
[0227] The light conversion layer 130 is spaced apart from the LED
light source 110 by a predetermined distance and converts light
emitted from the LED light source 110 to white light, which is then
transmitted to the liquid crystal panel 500.
[0228] The light conversion layer 130 includes the polymer
composite including a light emitting particle, for example a
quantum dot. Details of the polymer composite are the same as set
forth above.
[0229] The backlight unit 100 may further include a diffusion plate
on the light guide panel 120, and the light conversion layer 130
may be disposed between the light guide panel and the diffusion
plate, or on a side of the diffusion plate opposite the light guide
panel. Materials and structures for each of the LED light source
110, the light guide panel 120, the diffusion plate, and the liquid
crystal panel 500 are known in the art and are commercially
available, and thus are not particularly limited.
[0230] The polymer composite may be manufactured in the form of a
film. The film may be manufactured by using a mold or by casting to
have various thicknesses and forms. Alternatively, the polymer
composite may be prepared according to the process of FIG. 2. In
this case, the resin composition and/or quantum dot (QD)-containing
resin composition may include at least one additive selected from a
zinc compound, an indium compound, ascorbic acid or a salt thereof,
citric acid or a salt thereof, a tocopherol, and a tocotrienol.
[0231] When the light emitted from the LED light source 110 is
passed through the light conversion layer 130, blue light, green
light, and red light are mixed to emit white light. By changing the
compositions and sizes of semiconductor nanocrystals in the light
conversion layer 130, the blue light, green light, and red light
may be controlled in a ratio as desired, so as to provide white
light which provides excellent color reproducibility and color
purity. The white light may have color coordinates where Cx is
about 0.2 to about 0.56 and Cy is about 0.2 to about 0.42 in a CIE
1931 chromaticity diagram. As evidenced from the results, the
additive does not cause any changes of color coordinates of the
light conversion layer including the polymer composite.
[0232] In an embodiment, the light conversion layer 130 may include
a plurality of layers. In an embodiment, the plurality of layers
may be disposed so that the light emitting wavelength becomes
longer in a direction towards the LED light source 110. For
example, if the LED light source 110 is a blue LED light source,
the light conversion layer 130 may include a red light conversion
layer and a green light conversion layer that are sequentially
stacked in a direction away from the LED light source 110.
[0233] Even though not shown in FIG. 5, on the light conversion
layer 130, a film, e.g., a diffusion plate, a prism sheet, a
microlens sheet, a brightness enhancement film (e.g., a double
brightness enhancement film ("DBEF")), or a combination thereof,
may be further disposed. In addition, the light conversion layer
130 may be disposed between at least two films, e.g., a light guide
panel, a diffusion plate, a prism sheet, a microlens sheet, a
brightness enhancement film (e.g., a double brightness enhancement
film ("DBEF")), or a combination thereof.
[0234] FIG. 6 is a schematic view of a liquid crystal display
device 20 including the backlight unit 100 according to another
embodiment.
[0235] As shown in FIG. 6, a light conversion layer 130 may include
a film 131 including the polymer matrix and the semiconductor
nanocrystal, and at least one of a first polymer film 133 and a
second polymer film 135 may be disposed on at least one surface of
the film 131. The second polymer film 135 disposed under the film
131 may act as a barrier for preventing degradation of the
semiconductor nanocrystal caused by the LED light source 120.
[0236] The first polymer film 133 and the second polymer film 135
may include a polyester, a cyclic olefin polymer ("COP"), a second
polymer product produced by polymerization of the first monomer
including at least two thiol (--SH) groups, each located at a
terminal end of the first monomer, and the second monomer including
at least two unsaturated carbon-carbon bonds at a terminal end of
the second monomer, or a combination thereof. The polyester may
include polyethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, or the like, or a combination thereof.
The cyclic olefin polymer may be a polymer produced by chain
copolymerization of a cyclic monomer, such as a norbornene or a
tetracyclododecene, with a linear olefin monomer such as ethylene.
In an embodiment, the polymerized product of the first monomer
including at least two thiol (--SH) groups, each located at a
terminal end of the first monomer, and the second monomer including
at least two unsaturated carbon-carbon bonds at a terminal end of
the second monomer may be the same as set forth above.
[0237] At least one of the first polymer film 133 and the second
polymer film 135 may further include an inorganic oxide. The
inorganic oxide may include silica, alumina, titania, zirconia, or
a combination thereof. The inorganic oxide may act as a light
diffusion material. The inorganic oxide may be coated with a
thickness of about 10 nm to about 100 nm on a surface of at least
one of the first polymer film 133 and the second polymer film
135.
[0238] The first polymer film 133 may have a concavo-convex pattern
having a predetermined size on the surface opposite, e.g., not
contacting, the film 131 including a polymer matrix and
semiconductor nanocrystal. The second polymer film 135 may also
have a concavo-convex pattern having a predetermined size on the
surface opposite, e.g., not contacting, the film 131 including a
polymer matrix and semiconductor nanocrystal. The first polymer
film 133 and the second polymer film 135, with the concavo-convex
pattern thereon, may suitably diffuse light emitted from the LED
light source 110. Accordingly, the liquid crystal display device
may omit a diffusion plate or a prism sheet that may be present on
the light guide panel 120 in other embodiments. However, according
to another embodiment, the diffusion plate or a prism sheet may be
disposed on the light guide panel 120.
[0239] Even though not shown in FIG. 6, a film, e.g., a diffusion
plate, a prism sheet, a microlens sheet, and a brightness
enhancement film (e.g., a double brightness enhancement film
("DBEF")), or a combination thereof, may be further disposed on the
light conversion layer 130. In addition, the light conversion layer
130 may be disposed between at least two films, e.g., a light guide
panel, a diffusion plate, a prism sheet, a microlens sheet, a
brightness enhancement film (e.g., a double brightness enhancement
film ("DBEF")), or a combination thereof.
[0240] The white light emitted from the backlight unit, e.g., the
backlight unit 100, is incident toward the liquid crystal panel
500. The liquid crystal panel 500 provides a predetermined color
image using the white light incident from the backlight unit 100.
The liquid crystal panel 500 may have a structure in which a first
polarizer 501, a liquid crystal layer 502, a second polarizer 503,
and a color filter 504 are sequentially disposed. The white light
emitted from the backlight unit, e.g., the backlight unit 100, is
transmitted through the first polarizer 501, the liquid crystal
layer 502, and the second polarizer 503 and then into the color
filter 504 to express a predetermined color image.
[0241] The liquid crystal panel is not particularly limited, and
any liquid crystal panel that is known in the art or is
commercially available may be included. Details for the liquid
crystal display device are the same as set forth above.
[0242] Hereinafter, the embodiments are illustrated in more detail
with reference to examples. However, they are exemplary embodiments
of the present disclosure, and the present disclosure is not
limited thereto.
EXAMPLES
Reference Example
Production of Bare Semiconductor Nanocrystals
[0243] (1) 0.2 millimoles (mmol) of indium acetate, 0.6 mmol of
palmitic acid, and 10 milliliters (mL) of 1-octadecene are placed
in a flask. The flask is evacuated at 120.degree. C. for one hour,
filled with nitrogen gas (N.sub.2), and heated to 280.degree. C. A
mixed solution of 0.1 mmol of tris(trimethylsilyl)phosphine
(TMS.sub.3P) and 0.5 mL of trioctylphosphine (TOP) is quickly
injected thereto, and a reaction is allowed to proceed for 20
minutes. The reaction mixture is then rapidly cooled and acetone is
added thereto to produce nanocrystals, which are then separated by
centrifugation and dispersed in toluene. The first absorption
maximum in UV-VIS spectrum of the InP core nanocrystals thus
prepared is in the range of 420-600 nm.
[0244] 0.3 mmol (0.056 gram (g)) of zinc acetate, 0.6 mmol (0.189
g) of oleic acid, and 10 mL of trioctylamine are placed in a flask.
The flask is evacuated at 120.degree. C. for 10 minutes, filled
with nitrogen gas (N.sub.2), and heated to 220.degree. C. A toluene
dispersion of the InP core nanocrystals thus prepared (optical
density: 0.15) and 0.6 mmol S/TOP are added to the flask and the
resulting mixture is heated to 280.degree. C. The reaction is
allowed to proceed for 30 minutes. After the reaction is ceased,
the reaction solution is quickly cooled to room temperature to
obtain a reaction mixture including InP/ZnS semiconductor
nanocrystals.
[0245] (2) An excessive amount of ethanol is added to the reaction
mixture including the InP/ZnS semiconductor nanocrystals, which is
then subjected to centrifugation to remove excess organic material
on the surface of the nanocrystals. After centrifugation, the
supernatant is discarded and the precipitate obtained from the
centrifugation is dried and dispersed in chloroform. A UV-vis
absorption spectrum of the resulting dispersion is measured. The
prepared nanocrystal emits red light or green light.
Example 1
Preparation of Polymer Composition and Natural Curing of Prepared
Composition
[0246] 100 parts by weight of a monomer mixture including
pentaerythritol tetrakis(3-mercaptopropionate) (4T), tricyclodecane
dimethanol diacrylate (A-DCP), and lauryl methacrylate (LMA) are
prepared. The monomers are mixed in a mole ratio of 1:1.52 between
a thiol group and an acrylate group in the monomer mixture. Then,
0.5 parts by weight of Irgacure 184 and 0.5 parts by weight of
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) are added to
100 parts by weight of the monomer mixture. The finally obtained
mixture is defoamed under vacuum.
[0247] Ascorbic acid, citric acid, zinc acetate, zinc stearate,
ZnF.sub.2, Zn metal, or indium acetate (In(OAc).sub.3) is added to
the monomer mixture in an amount set forth in Table 1 per 100 parts
by weight of the monomer mixture. In Table 1, the 184 and TPO as a
photoinitiator respectively indicate Irgacure 184 and
trimethylbenzoyl diphenyl phosphine oxide that is commercially
available from BASF Co. Ltd.
[0248] Viscosity of the composition is measured at room temperature
by using a viscometer (a 50 millimeters (mm) cone spindle, Anton
Paar).
[0249] The composition is stored under conditions provided in Table
1.
[0250] After the storage, whether the composition is cured or not
or whether the viscosity is changed or not, the appearance of the
composition is examined, and the viscosity of the composition is
measured by the above method. The results are compiled in Table
1.
TABLE-US-00001 TABLE 1 Additive and amount (additive weight based
on 100 parts by weight of resin Initial Storage Changes of
viscosity composition) viscosity condition after storage Ascorbic
acid 120-130 cps 20.degree. C./ No changes of viscosity (1 part by
weight) 12 hours Citric acid No changes of viscosity (1 part by
weight) Zn (1 part by weight) 40.degree. C./ No changes of
viscosity acetate (0.03 parts by weight) 34 hours No changes of
viscosity (0.01 part by weight) 128 cps, No changes of viscosity
ZnO 20.degree. C./ No changes of viscosity (0.5 to 1 part by
weight) 12 hours Zn stearate 123 cps, No changes of (0.03 parts by
weight) viscosity ZnF.sub.2 No changes of viscosity (1 part by
weight) Zn metal No changes of viscosity (1 part by weight)
Zn(Et).sub.2 No changes of viscosity (1 part by weight)
In(OAc).sub.3 No changes of viscosity (1 part by weight) Zink
acetate 40.degree. C./ No changes of viscosity (0.02 parts by
weight) 54 hours
[0251] As shown in Table 1, when the above additive is added, a
curing prevention effect is clearly found.
Comparative Example 1
Preparation of Polymer Composition and Evaluation as to Whether a
Natural Curing Occurs for the Prepared Composition
[0252] Acetic acid, oleic acid, stearic acid, palmitic acid, water,
ZnCl.sub.2, cadmium acetate, or copper acetate is added to the
monomer mixture in an amount set forth in Table 2 per 100 parts by
weight of the monomer mixture to provide a composition. In Table 2,
the 184 and TPO as a photoinitiator respectively indicate Irgacure
184 and trimethylbenzoyl diphenyl phosphine oxide commercially
available from BASF Co., Ltd.
[0253] Viscosity of the composition is measured at room temperature
using a viscometer (a 50 mm cone spindle, Anton Paar).
[0254] The composition is stored under conditions set forth in
Table 2.
[0255] After the storage, whether the composition is cured or not
or whether the viscosity is changed or not is examined by observing
appearance of the composition or measuring viscosity of the
composition in the aforementioned method, and the results are
compiled in Table 2.
TABLE-US-00002 TABLE 2 Additive and amount (additive weight based
on 100 parts by weight Initial Storage Changes of viscosity of
resin composition) viscosity condition after storage
CH.sub.3CO.sub.2H 120-130 20.degree. C./12 538 cps, viscosity (1
part by weight) centipoise hours increase Oleic acid (cps) Curing
is processed (1 to 2 parts by weight) Steric acid Curing is
processed (1 part by weight) Palmitic acid Curing is processed (1
part by weight) H.sub.2O Curing initiates from (1 part by weight)
the bottom ZnCl.sub.2 Cured (0.0075 parts by weight) Cd(OAc).sub.2
Curing is processed 1 part by weight Cu(OAc).sub.2 Curing is
processed 1 part by weight
[0256] Referring to the results of Table 2, cadmium salt and copper
salt have no curing prevention effect. In addition, zinc chloride
has no curing prevention effect. Furthermore, fatty acids such as
oleic acid, stearic acid, and palmitic acid have no curing
prevention effect. In addition, water has no curing prevention
effect.
Example 2
Determination of Causes of Curing Phenomenon of the Quantum Dot
Polymer Composition and Effects of Curing Inhibiting Additives
[0257] It is believed that a quantum dot polymer composition may
undergo curing when the reactants used during quantum dot (QD)
synthesis are not thoroughly removed in a separation process of the
quantum dots (QD) via a non-solvent precipitation method. Examples
of the unremoved reactant that may cause the curing may include
trioctylphosphine (TOP) or sulfur-coordinated trioctylphosphine
(S/TOP). The liquid chromatography-mass spectroscopy (LC-MS)
analysis of a QD precipitate may confirm that the amount of the
S/TOP remaining on the QDs tends to decrease as the number of
precipitation/separation increases. To determine whether the curing
is caused by the unremoved reactant, the following experiments are
conducted: TOP or S/TOP is added to the monomer composition and the
effect of a zinc compound on curing inhibition of the resulting
composition is observed.
[0258] A composition including a monomer mixture of pentaerythritol
tetrakis(3-mercaptopropionate) (4T), tricyclodecane dimethanol
diacrylate (A-DCP), lauryl methacrylate (LMA), trimethylolpropane
triacrylate (TMPTA), Irgacure 184, and
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) is prepared.
2 parts by weight of an initiator is used based on 100 parts by
weight of the monomer mixture. In the monomer mixture, the mole
ratio of the thiol and the acrylate is thiol:acrylate=1:1.77. Then,
TOP or a 2 molar (M) S/TOP solution obtained by dissolving sulfur
in TOP is added to the monomer mixture in an amount of 0.01 mmol
per 1 g of the total weight of the monomer mixture, to which zinc
stearate is added in an amount set forth in Table 3.
[0259] Viscosity of the composition thus prepared is measured in
the same manner set forth in Example 1.
[0260] Some compositions are cured immediately after the mixing
process. The composition that does not show curing phenomenon
directly after the mixing is stored under conditions set forth in
Table 3, and then its viscosity is measured. The results for each
composition are compiled in Table 3.
TABLE-US-00003 TABLE 3 Amount of zinc stearate Curing relative to
curing Viscosity components components (mole ratio) Storage
condition (cps) TOP 10 room temperature/3 h 171 (trioctylphosphine)
40.degree. C./85% RH/1 day 226 2.45 Immediately when being Partial
curing mixed 1 Immediately when being Curing mixed 0.45 Immediately
when being Curing mixed 2M 0.45 Room temperature/3 h 130 S/TOP
40.degree. C./85% RH/1 day 175 0.1 room temperature/1 h 160 0.02
Immediately when being Partial curing mixed 0.01 Immediately when
being Curing mixed
[0261] The results of Table 3 confirm that the curing may be
inhibited with the increase in the amount of zinc stearate per the
amount of the curing-causing component (i.e., TOP or 2 M S/TOP),
which implies that the addition of the zinc compound may suppress
the curing phenomenon caused by TOP or S/TOP being able to remain
in a QD resin.
Example 3
Evaluation of the Influence of the Additives on Light Emitting
Characteristics (in Case where the Curing Inhibitor is Added to a
Filling Resin)
[0262] A mixture including pentaerythritol
tetrakis(3-mercaptopropionate) (4T) as a first monomer, lauryl
methacrylate (LMA) and tricyclodecane dimethanol diacrylate (A-DCP)
as a second or a fourth monomer, and 0.5 parts by weight of
Irgacure 184 and 0.5 parts by weight of
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) as an
initiator per 100 parts by weight of the mixture are mixed together
to obtain a monomer mixture. The monomer mixture including 4T and
(LMA+A-DCP) in a ratio of 3:7 is used as a Ref. composition, and a
composition A is prepared by adding 200 parts per million (ppm) of
zinc acetate based on 1 part by weight of the monomer mixture of
4T:(LMA+A-DCP) in a ratio of 3:7. The Ref. composition and the
composition A are used as a filling resin composition in the
manufacture of the QD film.
[0263] A monomer for a quantum dot resin is prepared by mixing 100
parts by weight of a mixture of pentaerythritol
tetrakis(3-mercaptopropionate) (4T) as a first monomer,
laurylmethacrylate (LMA), trimethylolpropane triacrylate (TMPTA),
and tricyclodecane dimethanol diacrylate (A-DCP) as a second or a
fourth monomer (the mole ratio between the first monomer and the
second and the fourth monomers=1:3), 1 part by weight of Irgacure
184 and 1 part by weight of
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) as
initiators, and 4 parts by weight of ZnO. A solution including the
red light emitting InP/ZnS quantum dot or green light emitting
InP/ZnS quantum dot (QD) each prepared in Reference Example 1 is
added to acetone and ethanol to precipitate the QDs, which are then
dried and added to the aforementioned monomer mixture in an
appropriate manner (e.g., as a dispersion). The resulting mixture
is vortexed to produce a quantum dot-containing composition
(hereinafter, referred to as the quantum dot resin
composition).
[0264] The quantum dot resin composition is coated on a soft mold
to obtain a QD-containing monomer composition film, a barrier film
(a silica-coated PET film) is formed thereon and compressed, and
the QD-containing composition layer is cured by radiating UV rays
(wavelength: less than or equal to 365 nm, intensity: 500
mJ/cm.sup.2), obtaining a quantum dot-resin composite. The quantum
dot-resin composite is released from the soft mold as a layer
attached on the barrier film. Then, the filling resin composition
(i.e., the Ref. composition or composition A) is coated over the
QD-resin composite layer and cured by UV irradiation (wavelength:
less than or equal to 365 nm, intensity: 500 milliJoules (mJ)) to
produce a quantum dot resin composite film coated with the filling
resin. Another quantum dot resin composite film coated with the
filling resin composition is manufactured in the same manner as set
forth above. The two obtained films are integrated with each
filling resin layer facing each other to produce a final QD
film.
[0265] The obtained film (8.times.8 cm) is analyzed on a blue light
source (a 60 inch TV panel) by using a spectroradiometer (CS-2000,
Konica Minolta), and the results are shown in FIG. 3. Luminance
value (Lv) of the film is measured at a color coordinate of
Cy=0.24, and the results are provided in Table 4.
TABLE-US-00004 TABLE 4 Cy = 0.24 Application of filling resin
Relative Additive Lv comparison Cx Cy No additive (Comparative 340
100 0.2340 0.2400 Example) Zinc acetate 200 ppm 332 98 0.2341
0.2400 (composition A)
[0266] Referring to FIG. 3 and Table 4, the brightness (the
luminance value) of the film manufactured by using composition A
including an additive as a filling resin and the brightness of the
film manufactured by using a composition including no additive show
no substantial difference.
Example 4
Evaluation of the Influence of the Additives on Light Emitting
Characteristics (in Case where the Curing Inhibitor is Added to a
QD Resin)
[0267] 100 parts by weight of a mixture including pentaerythritol
tetrakis(3-mercaptopropionate) (4T) as a first monomer,
laurylmethacrylate (LMA) and tricyclodecane dimethanol diacrylate
(A-DCP) as a second or fourth monomer, and 0.5 parts by weight of
Irgacure 184 and 0.5 parts by weight of
2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) as initiators
are mixed and the resulting mixture is used as a filling resin
composition.
[0268] A quantum dot resin composition is prepared to include 100
parts by weight of a monomer mixture including pentaerythritol
tetrakis(3-mercaptopropionate) (4T) as a first monomer and lauryl
methacrylate (LMA), trimethylolpropane triacrylate (TMPTA), and
tricyclodecane dimethanol diacrylate (A-DCP) as a second or fourth
monomer (at a ratio of the first monomer and the second and the
fourth monomers=1:3), 1 part by weight of Irgacure 184 and 1 part
by weight of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO)
as initiators together with 4 parts by weight of ZnO.sub.2.
[0269] A solution including the red light emitting InP/ZnS quantum
dot or the green light emitting InP/ZnS quantum dot (QD) each
prepared in Reference Example 1 is added to acetone and ethanol to
precipitate the QDs, which are then dried and added to the
aforementioned quantum dot resin composition in an appropriate
manner (e.g., as a dispersion). The resulting mixture is vortexed
to produce a quantum dot-containing composition (hereinafter,
referred to as the Ref. quantum dot resin composition).
[0270] Quantum dot-containing composition A is prepared in
substantially the same manner as the method of manufacturing the
Ref. quantum dot-containing composition, except that 0.63 parts by
weight of zinc stearate is added per 100 parts by weight of the
monomer mixture.
[0271] Quantum dot-containing composition B substantially the same
manner as the method of manufacturing the Ref. quantum
dot-containing composition, except that 0.26 parts by weight of
indium acetate is added per 100 parts by weight of the monomer
mixture.
[0272] The filling resin composition is commonly used and each of
the Ref. quantum dot resin composition, Quantum dot-containing
composition A, and Quantum dot-containing composition B is used to
manufacture a QD film in the same manner as set forth in Example 3.
The obtained QD film (8.times.8 centimeters (cm)) is analyzed on a
blue light source (a 60 inch TV panel) using a Spectroradiometer
(CS-2000, Konica Minolta), and the results are shown in FIG. 4. The
luminance value (Lv) of the film is measured at a color coordinate
Cy=0.24, and the results are compiled in Table 5.
TABLE-US-00005 TABLE 5 Cy = 0.24 Relative Lv comparison Cx Cy Ref.
QD film using quantum dot 341 100 0.2287 0.2400 resin composition
QD film using quantum dot resin 336 99 0.2298 0.2399 composition A
QD film using quantum dot resin 345 101 0.2273 0.2399 composition
B
[0273] The results of FIG. 4 and Table 5 confirm that the films
manufactured by using Quantum dot resin composition A including an
additive and Quantum dot resin composition B including an additive
show a luminance value that is substantially the same as that of
the film manufactured by using the Ref. quantum dot resin
composition.
[0274] While this disclosure has been described in connection with
what is presently considered to be practical exemplary embodiments,
it is to be understood that the disclosure is not limited to the
disclosed embodiments, but, on the contrary, is intended to cover
various modifications and equivalent arrangements included within
the spirit and scope of the appended claims.
* * * * *